Silver halide color photographic material and discoloration inhibitor therefor

ABSTRACT

There is provided a silver halide color photographic material containing a 6-hydroxychroman derivative in, combination with a specific coupler, i.e., a 5-pyrazolone type magenta coupler having an --SR group at the coupling position or a 5-pyrazolone type magenta coupler having an anilino group at the 3-position. The photosensitive material provides photographic images, quality of which is prevented from deteriorating as time passes. The photographic color images are free from discoloration or fading and do not form yellow stains on a white background.

BACKGROUND OF THE INVETNION

1. Field of the Invention

The present invention relates to a silver halide color photographicmaterial. More particularly, it relates to a color photosensitivematerial which is so designed as to prevent dye images eventuallyobtained by development from fading or discoloration andnoncolor-developed portions (hereafter referred to as "whitebackground") from discoloration.

2. Description of the Prior Art

Generally photographic images formed by a silver halide photographicmaterial does not keep its quality permanently, but it deteriorates astime lapses during preservation. This is particularly true of colorphotography having images made up of azomethine dyes or indoaniline dyesformed by a reaction of a coupler with oxidation products of thearomatic primary amine developing agents. Such color photographyundergoes discoloration or fading of dye images and discoloration of awhite background when exposed to light for a prolonged period of time orpreserved under heat and humidity exposure conditions.

The deterioration of the quality of image is detrimental to a recordingmaterial. In order to prevent the image from deterioration, there havebeen made a large number of proposals. The most effective proposal amongthem is to use a color image stabilizer in combination with a coupler. Aphenolic compound is the typical example of such a compound. Thecompound having the ether linkage at the p-position is relatively highin the prevention of discoloration effect. Examples of such compoundsare alkoxy- or aryloxyphenols, hydroxycoumarans, hydroxychromans, andhydroxyspirochromans as disclosed in U.S. Pat. Nos. 3,432,300,3,573,050, 3,574,627, 3,698,909, 3,764,337, 3,930,866, 4,120,723,4,113,488, 4,264,720, and 4,388,404; British Pat. No. 2,066,975 (B);West Germany Pat. (OLS) Nos. 2,146,668 and 2,726,283; Japanese PatentApplication (OPI) Nos. 14023/1976, 124926/1976, and 53321/1978; andJapanese Patent Publication Nos. 20537/1981. 40817/1981, and 10539/1984.

Another compounds known in the art are phenolic compounds having theether linkage at the p-position in which the hydroxyl group isetherified or silyletherified, as disclosed in U.S. Pat. Nos. 4,155,765,4,254,216, and 4,279,990.

Although these compounds are effective in preventing color images fromfading and/or discoloration, they are still unsatisfactory as a colorimage stabilizer which must satisfy several requirements forphotography. Some of them are less in effectiveness and deleterious tothe hue even though they are effective against discoloration, and otherscause fogging, poor dispersion, or crystallization.

Among the phenolic compounds having the ether linkage at the p-position,α-tocopherol is known as a natural antioxidant while 6-hydroxychroman isknown as a compound effective for the prevention of discoloration asdisclosed in U.S. Pat. Nos. 3,432,300 and 3,698,909; and Japanese PatentApplication (OPI) No. 10539/1984.

U.S. Pat. No. 4,113,495 discloses compounds having hydroquinone at the2-position of the chroman ring, and U.S. Pat. No. 4,264,720 disclosescompounds having hydroquinone diether at the 2-position of the chromanring.

As a result of the recent improvement in color photographic materialswhich require more sophisticated properties in the color photography,the compounds disclosed in the above-mentioned patents are considered tobe unsatisfactory in the preservability of photographic images. In otherwords, the compounds are not effective to prevent the change ofphotographic image density, the change of color balance of yellow,magenta, and cyan after discoloration, and the staining of the whitebackground which occur due to light, heat, and moisture duringpreservation of the photography.

BRIEF SUMMARY OF THE INVENTION

Accordingly, it is a first object of the present invention to provide asilver halide color photographic material which contains a stabilizer toprevent quality of photographic images from deteriorating as timepasses.

It is a second object of the invention to provide a color photographicmaterial which incorporates a stabilizer in an emulsion layer which iseffective to prevent the color photographic images from fading ordiscoloring without causing hue change and fogging, thereby obtainingstabilized photographic color images.

It is a third object of the invention to provide a color photographicmaterial which is free from discoloration and fading of photographiccolor images and any loss in the density of formed dyes in the colorimages.

It is a fourth object of the invention to provide a color photographicmaterial which incorporates a stabilizer in a photographic layer anddoes not form yellow stains on unexposed portions of the photosensitivematerial when the photographic color image is exposed to light, heat,and moisture after development processing.

It is a fifth object of the invention to provide a color photographicmaterial which is less in fading or discoloration over the entiredensity range of photographic color image formed by developmentprocessing and underwent no change in color balance.

It is a sixth object of the invention to provide an antioxidant which,because of its high antioxidant action which can be applied to theprevention of fading and discoloration of photographic color imagesformed by the subtractive color process and also applied to dyes,rubbers, plastics, and petroleum products and the like.

Other and further objects, features, and advantages of the inventionwill appear more fully from the following description.

DETAILED DESCRIPTION OF THE INVENTION

According to this invention, there is provided a silver halide colorphotographic material which contains a compound represented by formula(I) below.

In addition, according to this invention, there is provided a silverhalide photosensitive material for color photography which contains atleast one kind of the compound represnted by the formula (I) below andat least one kind of the pyrazolone type magenta coupler. ##STR1##wherein R₁ and R₂ each independently denotes a hydrogen atom, alkylgroup, cycloalkyl group, heterocyclic group, trialkylsilyl group,alkanesulfonyl group, arylsulfonyl group, or --X--Y with the provisothat one of R₁ and R₂ is a hydrogen atom and that both R₁ and R₂ cannotbe hydrogen atoms at the same time and X denotes a ##STR2## group, and Ydenotes an alkyl group, cycloalkyl group, aryl group, alkoxy group,aryloxy group, alkylamino group, dialkylamino group, arylamino group,diarylamino group, alkyloxycarbonyl group, aryloxycarbonyl group, oracyl group. R₃, R₄, and R₅, which may be the same or different, eachindependently denotes a hydrogen atom, alkyl group, cycloalkyl group,alkenyl group, aryl group, alkoxy group, aryloxy group, alkenoxy group,alkylthio group, arylthio group, acylamino group, diacylamino group,sulfoneamide group, alkylamino group, acyl group, alkoxycarbonyl group,acyloxy group, or halogen atom. If R₁, R₂, R₃, R₄, and R₅ are alkylgroups or aryl groups or those groups containing partially alkyl groupsor aryl groups, such alkyl groups or aryl groups may be furthersubstituted.

The compounds represented by formula (I) are preferably those which arerepresented by formula (X) below. ##STR3## wherein R₃ has the samemeaning as in formula (I); and R₂₃ and R₂₄ each denote a hydrogen atomor alkyl group, provided that both of them are not hydrogen atoms oralkyl groups at the same time.

Preferably one of R₂₃ and R₂₄ is an alkyl group and the other is ahydrogen atom. R₃ should preferably be a methyl group from thestandpoint of synthesis.

According to one embodiment of this invention, a compound represented byformula (I) above is combined with a pyrazolone type magenta couplerhaving at the coupling position a group represented by formula (II)below, providing remarkable improvements of fastness to light, heat, andhumidity.

Formula (II)

    --S--R

wherein R denotes an alkyl group or aryl group, the alkyl groupincluding linear or branched alkyl groups, aralkyl groups, alkenylgroups, cycloalkyl groups, and cycloalkenyl groups (e.g., n-dodecylgroup, t-octyl group, benzyl group, cyclopentyl group, and cyclohexenylgroup), and the aryl group including phenyl groups and naphthyl groups.

The 5-pyrazolone type magenta coupler having at the coupling position agroup represented by formula (II) includes, for example, a compoundrepresented by formula (III) below. ##STR4## wherein R is defined as informula (II); Ar₁ denotes an aryl group; and Z denotes an acylaminogroup, anilino group, or ureido group.

The coupler represented by formula (III) is added in an amount of 2×10⁻³to 5×10⁻¹ mol, preferably 1×10⁻² mol or more.

The compounds represented by formula (III) are preferably thosecompounds represented by formula (IV) below. ##STR5## wherein R has thesame meaning as in formula (II); Ar₂ denotes a phenyl group having atleast one substituent selected from a halogen atom, alkyl group, alkoxygroup, alkoxycarbonyl, or cyano group; R₆ denotes a halogen atom oralkoxy group; and R₇ denotes a hydrogen atom, halogen atom, alkyl group,alkoxy group, acylamino group, sulfoneamide group, sulfamoyl group,carbamoyl group, diacylamino group, alkoxycarbonyl group, alkoxysulfonylgroup, aryloxysulfonyl group, alkanesulfonyl group, arylsulfonyl group,alkylthio group, arylthio group, alkyloycarbonylamino group, alkylureidogroup, acyl group, nitro group, carboxyl group, or trichloromethylgroup; l is an integer of 1 to with the proviso when l is greater than1, the groups represented by R₇ may be the same or different.

The compounds represented by formula (IV) are preferably those compoundsin which --SR is the group represented by formula (V), (VI), or (VII)below. ##STR6## wherein R₈ denotes a halogen atom, hydroxyl group, alkylgroup, alkoxyl group, or aryl group; R₉ denotes a hydrogen atom, halogenatom, hydroxyl group, alkyl group, alkoxyl group, or aryl group with theproviso that at least one of R₈ and R₉ is an alkoxyl group; R₁₀ denotesan alkyl group or aryl group; R₁₁ denotes a halogen atom, alkyl group,alkoxyl group, or aryl group; m is an integer of 1 to 4, and n is aninteger of 1 to 5 with the proviso that when m or n is greater than 1,the groups represented by R₉ or R₁₁ may be the same or different; R₁₂denotes a hydrogen atom, alkyl group, or aryl group; R₁₃ denotes ahydrogen atom, alkyl group, aryl group, alkoxyl group, aryloxy group,alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylgroup, or carboxyl group; X₁ denotes an alkylene group, alkenylenegroup, arylene group, ##STR7## R₁₄ denotes a hydrogen atom, alkyl group,aryl group, or heterocyclic group. The sum of number of carbon atoms ofR₁₃ and R₁₄ should preferably be 12 and up, and either R₁₂ or R₁₃ maycombine with R₁₄ to form a 5- or 7-membered ring.

The compounds represented by formula (IV) are preferably those compoundsrepresented by formula (VIII) below. ##STR8## wherein Ar₂, R₆, and R₇are defined as in formula (IV); R₉ and m are defined as in formula (V);R₁₅ denotes an aliphatic group or aromatic group which may have (a) ahalogen atom, (b) a cyano group, (c) an aliphatic, aromatic, orheterocyclic, sulfonyl group, sulfinyl group, or sulfonyl group, (d)##STR9## or (e) -(A₂ -M)_(m) B₂, wherein A₁ denotes a single bond,oxygen atom, sulfur atom, imino group, or divalent aliphatic, aromatic,or heterocyclic group; B₁ denotes a hydroxyl group, aliphatic oraromatic oxy group, hydrogen atom, aliphatic group, aromatic group,heterocyclic group, or acyclic amino group or hydrazino group which mayhave a substituent group; A₂ denotes a single bond, or divalentaliphatic, aromatic, or heterocyclic group; B₂ denotes a hydrogen atom,aliphatic group, aromatic group, or heterocyclic group; M denotes anoxygen atom, sulfur atom, or imino group; and m denotes an integer of 1to 4.

In this invention, a coupler preferable to the unsubstituted is the onerepresented by formula (VIII) having an aliphatic oxy or aromatic oxygroup further substituted with at least one of the groups (a) to (e)given above.

R₉ and R₁₅ may be contiguous to each other forming a bis compound.

The "aliphatic group" as used herein denotes a linear, branched, orcyclic alkyl, alkenyl, or alkynyl group which may be saturated orunsaturated.

In more detail Ar₂ may include a substituted phenyl group, and thesubstituent group includes a halogen atom (e.g., chlorine atom, bromineatom, and fluorine atom), alkyl group having 1 to 22 carbon atoms (e.g.,methyl group, ethyl group, tetradecyl group, and t-butyl group), alkoxylgroup having 1 to 22 carbon atoms (e.g., methoxy group, ethoxy group,octyloxy group, and dodecyloxy group), alkoxycarbonyl group having 2 to23 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, andtetradecyloxycarbonyl group), and cyano group.

Example of R₆ may include a halogen atom (e.g., chlorine atom, bromineatom, and fluorine atom) and alkoxyl group having 1 to 22 carbon atoms(e.g., methoxy group, octyloxy group, and dodecyloxy group).

Example of R₇ may include a hydrogen atom, halogen atom (e.g., chlorineatom, bromine atom, and fluorine atom), alkyl group (linear or branchedalkyl group, aralkyl group, alkenyl group, cycloalkyl group, andcycloalkenyl group, e.g., t-butyl group, t-octyl group, tetradecylgroup, benzyl group, allyl group, cyclopentyl group, and cyclohexenylgroup), alkoxyl group (e.g., methoxy group, ethoxy group,2-ethylhexyloxy group, and tetradecyloxy group), acylamino group (e.g.,acetamido group, benzamido group, butanamido group, tetradecanamidogroup, α-(2,4-di-tert-amylphenyloxy) acetamido group,α-(2,4-di-tert-amylphenoxy) butylamido group, α-(3-pentadecylphenoxy)hexanamido group, α-(4-hydroxy-3-tert-butylphenoxy) tetradecanamidogroup, 2-oxo-pyrrolidin-1-yl group, 2-oxo-5-tetradecylpyrrolidin-1-ylgroup and N-methyltetradecanamido group), sulfonamido group (e.g.,methanesulfonamido group, benzensulfonamido group, p-toluenesulfonamidogroup, octansulfonamido group p-dodecylbenzenesulfonamido group, andN-methyl-tetradecanesulfonamido group), sulfamoyl group (e.g.,N-methyl-sulfamoyl group, N-hexadecylsulfamoyl group,N-[3-(dodecyloxy)-propyl] sulfamoyl group,N-[4-(2,4-di-tert-amylphenoxy)butyl) sulfamoyl group, andN-methyl-tetradecylsulfamoyl group), carbamoyl group (e.g.,N-methylcarbamoyl group, N-octadecylcarbamoyl group,N-[4-(2,4-di-tert-amylphenoxy)butyl]carbamoyl group, andN-methyl-N-tetradecylcarbamoyl group), diacylamino group (e.g.,N-succinimido group, N-phthalimido group, 2,5-dioxo-1-oxazolidinylgroup, 3-dodecyl- 2,5-doxo-1-hydrantoinyl group, and3-(N-acetyl-N-dodecylamino) succinimido group), alkoxycarbonyl group(e.g., methoxycarbonyl group, tetradecyloxycarbonyl group, andbenzyloxycarbonyl group), alkoxysulfonyl group (e.g., methoxysulfonylgroup, octyloxysulfonyl group, and tetradecyloxysulfonyl group),aryloxysulfonyl group (e.g., phenoxysulfonyl group and2,4-di-tert-amylphenoxysulfonyl group), alkanesulfonyl group (e.g.,methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonylgroup, and hexandecanesulfonyl group), arylsulfonyl group (e.g.,benzenesulfonyl group and 4-nonylbenzenesulfony group). alkylthio group(e.g., ehtylthio group, hexylthio group, benzylthio group,tetradecylthio group, and 2-(2,4-di-tert-amylphenoxy)ethylthio group),arylthio group (e.g., phenylthio group and p-tolylthio group),alkyloxycarbonylamino group (e.g., ethyloxycarbonylamino group,benzyloxycarbonylamino group, and hexadecyloxycarbonylamino group),alkylureido group (e.g., N-methyl ureido group, N,N-dimethylureidogroup, N-mehtyl-N-dodecylureido group, N-hexadecylureido group, andN,N-dioctadecylureido group), acyl group (e.g., acetyl group, benzoylgroup, octadecanoyl group, and p-dodecanamidobenzoyl group), nitrogroup, carboxyl group, or trichloromethyl group. Among theabove-mentioned substituent groups, the alkyl group indludes those whichhave 1 to 36 carbon atoms and the aryl group includes those which have 6to 38 carbon atoms.

Examples of R₉ may include a halogen atom, alkyl group, alkoxyl group,acylamino group, ureido group, alkoxycarbonylamino group, imido group(synonymous with diacylamino group), sulfonamido group, sulfamoyl group,alkoxycarbonyl group, carbamoyl group, and alkylthio group which havethe same meanings as described for R₇ above. In addition, R₉ denotes ahydrogen atom, hydroxyl group, aryl group (e.g., phenyl group, α- orβ-naphthyl group, 2-chlorophenyl group, 4-acetamidophenyl group,4-tert-butylphenyl group, and 4-cyanophenyl group), amino group (e.g.,N-alkylamino group, N,N-dialkylamino group and anilino group (whereinN-alkylamino group includes N-butylamino group, N-(2-methoxyethyl)aminogroup, N-(2-methanesulfonylethyl)amino group, andN-(3-acetamidpropyl)amino group; N,N-dialkylamino group includingN-N-dibutylamino group, N,N-dihexylamino group,N,N-bis(2-ethylhexylamino) group, N,N-bis(2-hexansulfonylethylamino)group, N-ethyl-N-dodecylamino group, N,N-bis(3-phenoxypropylamino)group, N-ethyl-N-[2-(2,4-di-tert-amylphenoxy)ethylamino) group, andN,N-bis{2-[(4-tert-butylphenoxy)acetamide]ethyl} group; and anilinogroup including phenylamino group, 4-methoxyphenylamino group,N-ethylphenylamino group, 2,4-di-tert-phenylamino group,3-methanesulfonamidophenylamino group, and 2-chlorophenylamino group,sulfamoylamino group (e.g., N,N-dibutylsulfamoylamino group,N-ethyl-N-dodecylsulfamoylamino group, N-ethyl-N-anilinosulfamoylaminogroup, and N,N-bis(2-butane-sulfonylethyl)sulfamoylamino group), nitrogroup, acyl group (e.g., acetyl group, benzoyl group, hexanoyl group,2,4-di-tert-butylbenzoyl group, 2-hydroxybenzoyl group, anddecyloxyacetyl group), and cyano group.

Examples of R₁₅ may include a cyano group, halogen atom, ##STR10##wherein A₁, B₁, A₂, M, B₂, and m have the same meaning defined as above,or alkyl or aryl group having a sulfonyl, sulfinyl, or phosphonylsubstituent group. Preferable example is an alkyl or aryl group having asubstituent group selected from: ##STR11## wherein: R₁₆ denotes ahydrogen atom, alkyl group, aryl group, or hetero cyclic group. R₁₇ andR₁₈ independently denote a hydrogen atom, alkyl group, aryl group, orheterocyclic group, or groups which may be connected to each other toform a 5-, 6-, or 7-membered nitrogen-hetro ring. R₁₉ denotes a hydrogenatom or alkyl group. R₂₀ denotes an alkyl group, alkoxyl group, arylgroup, or aryloxy group. R₂₁ and R₂₂ independently denote a hydrogenatom, alkyl group, aryl group, or heterocyclic group. The alkyl groupand aryl group represented by R₁₆ to R₂₂ may have the substituent groupenumerated for R₇ and R₈.

R₁₅ should preferably be an alkyl group having the ether group, carbonylgroup, sulfonyl group, or phosphonyl group mentioned above.

The following are typical examples of the above-mentioned magentacouplers. ##STR12##

According to another embodiment of this invention, the compoundrepresented by formula (X) above is contained in the silver halidephotosensitive material for color photography containing at least onekind of pyrazolone type magenta couplers represented by formula (IX)below. ##STR13## wherein Ar₃ has the same meaning as Ar₁ in formula(III) above; R₂₅ has the same meaning as R₆ in formula (IV) above; andR₂₆ and R₂₇ have the same meaning as R₇ in formula (IV) above. Thesubstituent groups in Ar₃, R₂₅, R₂₆, and R₂₇ and the preferred or morepreferred example of Ar₃, R₂₅, R₂₆, and R₂₇ are the same as thoseenumerated for Ar₂, R₆, and R₇ in formula (IV). The compound representedby formula (IX) is used in the same amount as the compound representedby formula (III).

The following are examples of the pyrazolone type magenta couplerrepresented by formula (IX). ##STR14##

According to the present invention, the compound represented by formula(I) is added in an amount of 10 to 200 mol%, preferably 30 to 150 mol%based on the magenta coupler represented by formula (II) or (IX).

The compound represented by formula (I) should preferably becoemulsified with the magenta coupler.

In the following the compound represented by formula (I) is described indetail.

R₁ and R₂ in formula (I) include a hydrogen atom, alkyl group(preferably linear or branched alkyl group, aralkyl group, alkenylgroup, cycloalkyl group, and cycloalkenyl group having 20 or less carbonatoms, e.g., methyl group, n-butyl group, t-butyl group, n-octyl group,n-dodecyl group, n-hexadecyl group, benzyl group, allyl group,cyclopentyl group, and cyclohexenyl group), heterocyclic group (e.g.,tetrahydropyranyl group), trialkylsilyl group (e.g., trimethylsilylgroup and dimethyl-t-butylsilyl group), alkanesulfonyl group (preferablyalkanesulfonyl group having 20 or less carbon atoms, e.g.,methanesulfonyl group, propanesulfonyl group, t-octanesulfonyl group,and octadecanesulfonyl group), arylsulfonyl group (preferablyarylsulfonyl group having 20 or less carbon atoms, e.g., benzensulfonylgroup, α-naphthalenesulfonyl group, and p-methoxybenzenefulfonyl group)or --X--Y.

In more detail, Y in --X--Y is an alkyl group (preferably linear orbranched alkyl group, aralkyl group, alkenyl group, cycloalkyl group,and cycloalkenyl group having 20 or less carbon atoms, e.g., methylgroup, n-butyl group, t-octyl group, n-dodecyl group, n-hexadecyl group,benzyl group, allyl group, cyclopentyl group, and cyclohexenyl group),aryl group (preferably aryl group having 20 or less carbon atoms, e.g.,phenyl group, m-mitrophenyl group, o-chlorophenyl group, and α-naphthylgroup), alkoxyl group (preferably alkoxyl group having 20 or less carbonatoms, e.g., methoxy group, t-butoxy group, cyclohexyloxy group,n-dodecyloxy group, and n-octadecyloxy group), aryloxy group (preferablyaryloxy group having 20 or less carbon atoms, e.g., phenoxy group,2,4,6-trichlorophenoxy group, p-methoxyphenoxy group, o-chlorophenoxygroup, β-naphthyloxy group, and α-naphthyloxy group), alkylamino group(preferably alkylamino group having 20 or less carbon atoms, e.g.,methylamino group, ethylamino group, and n-octadecylamino group),dialkylamino group (preferably dialkylamino group having 30 or lesscarbon atoms, e.g., diethylamino group and dioctylamino group),arylamino group (preferably arylamino group having 20 or less carbonatoms, e.g., phenylamino group, p-nitrophenylamino group,p-methylphenylamino group, and α-naphthylamino group). diarylamino group(preferably diarylamino group having 30 or less carbon atoms, e.g.,N.N-diphenylamino group), alkyloycarbonyl group (preferablyalkyloxycarbonyl group having 20 or less carbon atoms, e.g., methoxycarbonyl group, t-butoxycarbonyl group, cyclohexyloxycarbonyl group, andn-octyloxycarbonyl group), aryloxycarbonyl group (preferablyaryloxycarbonyl group having 20 or less carbon atoms, e.g.,phenoxycarbonyl group, p-methoxyphenyloxycarbonyl group,m-nitrophenoxycarbonyl group, and o-chlorophenoxycarbonyl group), andacyl group (preferably acyl group having 20 or less carbon atoms, e.g.,acetyl group, butyryl group, valeryl group, pivaloyl group, andmyristoyl group). R₁ and R₂ are preferably hydrogen atoms or alkylgroups.

In more detail R₃, R₄, and R₅ each includes hydrogen atom, alkyl group(preferably linear or branched alkyl group, aralkyl group, alkenylgroup, cycloalkyl group, and cycloalkenyl group having 20 or less carbonatoms, e.g., methyl group, ethyl group, isopropyl group, t-butyl group,t-octyl group, t-hexadecyl group, benzyl group, allyl group, cyclopentylgroup, and cyclohexenyl group), aryl group (preferably aryl group having20 or less carbon atoms, e.g., phenyl group, p-methylphenyl group,p-methoxyphenyl group, p-octanamidophenyl group, o-chlorophenyl group,and α-naphthyl group), alkoxyl group (preferably alkoxyl group having 20or less carbon aroms, e.g., methoxy group, t-butoxy group, cyclohexyloxygroup, n-dodecyloxy group, n-octadecyloxy group, benzyloxy group, andallyloxy group), aryloxy group (preferably aryloxy group having 20 orless carbon atoms, e.g., phenoxy group, p-methylphenoxy group,p-methoxyphenox group, p-caproamidophenoxy group, o-chlorophenoxy group,m-nitrophenoxy group, and α-naphthyloxy group), alkylthio group(preferably alkylthio group having 20 or less carbon atoms, e.g.,methylthio group, t-butylthio group, n-hexylthio group, cyclohexylthiogroup, and n-octadecylthio group), arylthio group (preferably arylthiogroup having 20 or less carbon atoms, e.g., phenylthio group,p-methylphenylthio group, o-carboxyphenylthio group, o-methylphenylthiogroup, o-menthoxycarbonylphenylthio group and m-nitrophenylthio group),acylamino group (preferably acylamino group having 20 or less carbonaroms, e.g., acetylamino group, benzoylamino group, and caproaminogroup), diacylamino group (preferably diacylamino group having 30 orless carbon atoms, e.g., succinimido group and 3-hydantoinyl group),sulfonamido group (preferably sulfonamido group having 20 or less carbonatoms, e.g., methanesulfonamido group and benzenesulfonamido group),alkylamino group (preferably alkylamino group having 30 or less carbonatoms, e.g., ethylamino group t-butylamino group, dioctylamino group,and n-octadecylamino group), acyl group (preferably acyl group having 20or less carbon atoms, e.g., acetyl group, capryl group, andp-methoxybenzoyl group), alkyloxycarbonyl group (preferablyalkyloxycarbonyl group having 20 or less carbon atoms, e.g., methoxycarbonyl group, t-butoxycarbonyl group, and n-octadecyloxycarbonylgroup), acyloxy group (preferably acyloxy group having 20 or less carbonatoms, e.g., acetoxy group, caproxy group, lauroxy group, and benzoyloxygroup), and halogen atom (e.g., chlorine atom and bromine atom).

Among the groups defined above, those groups which have an alkyl groupor aryl group may further have a substituent group such as alkyl group,cycloalkyl group, alkenyl group, aryl group, benzyl group, halogen atom,nitro group, cyano group, hydroxyl group, alkyloxy group, cycloalkyloxygroup, alkenyloxy group, aryloxy group, benzyloxy group, alkylthiogroup, arylthio group, amino group, alkylamino group, acylamino group,sulfonamido group, alkoxycarbonyl group, silyl group, acyl group,acyloxy group, sulfamoyl group, and sulfonyl group, some of which havebeen described in the definition of formula (I) above.

The following are the typical examples of the compounds represented byformula (I). They are illustrative only, and should not be construed asrestricting the scope of the invention. ##STR15##

The compounds represented by formula (I) can be synthesized according tothe process described in U.S. Pat. No. 4,264,720.

The compound of formula (I) wherein R₁ is hydrogen, for example,2-(2-alkoxy-5-hydroxy-4-methylphenyl)-6-hydroxy-2,4,4,7-tetramethyl-chromanderivative, can be synthesized according to the following steps.##STR16##

Wherein R₂ has the same meaning as defined above.

As is shown in synthesis scheme (1) at first, compound 1 is convertedinto compound 2, which is then reacted with an alkylating agent to givecompound 4 having a varied aliphatic group represented by R₂. In thesynthesis process, compound 3 formed may be isolated before the reactionto form compound 4. Alternatively, the reaction may be carried out inthe same vessel without isolating compound 3.

Compound 1 can be synthesized according to the process described in U.S.Pat. No. 4,113,495.

The compound of formula (I) wherein R₂ is hydrogen, for example,2-(5-alkoxy-2-hydroxy-4-methylphenyl)-6-hydroxy-2,4,4,7-tetramethyl-chromanderivative, can be synthesized according to the following steps.##STR17##

Wherein R₁ has the same meaning as above.

As is shown in synthesis scheme (2), compound 10 produced from compound1 through several steps is reacted with an alkylating agent to givecompound 12 having a varied aliphatic group represented by R₁.

In the synthesis scheme (2), compounds 8 and 11 may be isolated beforethe subsequent reactions (8→9 or 11→12). Alternatively, the reaction maybe carried out in the same vessel without isolating compounds 8 and 11.

The compound represented by formula (I) should be added in an amount of10 to 200 mol%, preferably 30 to 150 mol% based on the magenta couplerof this invention. This compound should preferably be coemulsified withthe magenta coupler.

The compound represented by formula (I) in this invention may be used ina composition as the active ingredient with a diluent, solvent, carrier,and the like in a proper ratio. It may also include the chromandorivative alone.

The compounds represented by formula (I) in this invention may be usedindividually or in combination with one another. It may also be used incombination with a known discoloration inhibitor, which includes, forexample, hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans,spiro-coumarans, spiro-indanes, p-alkoxyphenols, bisphenoles, and otherhindered phenoles; gallic acid derivatives, methylenedioxybenzenes,aminophenols, hindered amines, and those compounds obtained bysilylating, acylating, or alkylating the phenolic hydroxyl group of saidcompounds; and metal complexes.

Preferred examples of the known discoloration inhibitors are disclosedin U.S. Pat. Nos. 3,336,135, 3,432,300, 3,573,050, 3,574,627, 3,700,455,3,764,337, 3,935,016, 3,9872,944, 4,254,216, and 4,279,990; British Pat.Nos. 1,347,556, 2,062,888, 2,066,975, and 2,077,455; Japanese PatentApplication No. 205278/1983, Japanese Patent Application (OPI) Nos.152225/1977, 17729/1978, 20327/1978, 145530/1979, 6321/1980, 21004/1980,24141/1983, and 10539/1984; and Japanese Patnet Publication Nos.31625/1973 and 12337/1979. It is preferable to use the compoundrepresented by formula (I) in combination with hydroquinones,6-hydroxychromans, p-alkoxyphenols, alkoxy-substituted spiro-indanes,methylenedioxybenzenes, or bisphenols.

The following are the typical examples of the known discolorationinhibitor preferred in this invention. ##STR18##

The effect attained in this invention can be enhanced when anultraviolet-light absorbent is employed. Preferred examples ofultraviolet-light adsorbents are benzotriazole compounds with an arylsubstituent (as disclosed in U.S. Pat. No. 3,533,794), 4-thiazolidonecompounds (as disclosed in U.S. Pat. Nos. 3,314,794 and 3,352,681),benzophenone compounds (as disclosed in Japanese Patent Application(OPI) NO. 2784/1971), cinnamic ester compounds (as disclosed in U.S.Pat. Nos. 3,705,805 and 3,707,375), butadiene compounds (as disclosed inU.S. Pat. No. 4,045,229), benzoxydole compounds (as disclosed in U.S.Pat. No. 3,700,455) and other compounds (as disclosed in U.S. Pat. No.3,499,762 and Japanese Patent Application (OPI) No. 48535/1979). Furthera coupler having ultraviolet-light absorbency (e.g., cyan-dyeformingcoupler of α-naphthol series) or a polymer having ultraviolet-lightabsorbency. The ultraviolet-light absorbent may be mordanted in aspecific layer of the color photographic material.

The ultraviolet-light absorbent may be added optionally to any layer inthe color photographic material. For example, it may be added to aninterlayer placed above (distant side from the support) the magentaimage-forming layer or protective layer or both. It may be added to acyan image-forming layer or an adjacent layer thereof.

The compound represented by formula (I) of this invention attains a muchenhanced effect in the prevention of discoloration when anultraviolet-light absorbent represented by formula (XI) below is addedto at least one layer of protective layers, being divided into two.##STR19## wherein R₃₁, R₃₂, R₃₃, R₃₄, and R₃₅, which may be the same ordifferent, each represents a hydrogen atom, halogen atom, nitro group,hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group,acyloxy group, aryloxy group, alkylthio group, arylthio group, mono- ordialkylamino group, acylamino group, or 5- or 6-membered heterocyclicgroup containing at least oxygen or nitrogen. R₃₄ and R₃₅ may formthrough ring closure a 5- or 6-membered aromatic ring composed of carbonatoms. These groups may have substituent groups thereon if they have anatom or group capable of being substrituted.

The following are typical examples of the ultraviolet-light absorbentsrepresented by the formula (XI). They are illustrative only and shouldnot be construed as restricting the scope of the invention. ##STR20##

The compounds represented by formula (XI) above may be synthesizedaccording to the processes as disclosed in Japanese Patent Application(OPI) Nos. 29620/1969, 151149/1975, and 95233/1979; U.S. Pat. No.3,766,205; EP No. 0057160; and Research Disclosure 22519 (1983, No.225). It is also possible to use polymeric UV absorbents as disclosed inJapanese Patent Application (OPI) Nos. 111942/1983, Japanese PatentApplication Nos. 61937/1982, 63602/1982, 129780/1982, and 133371/1982.An example thereof is indicated by UV-6. A low-molecule UV absorbent anda high-molecule UV absorbent may be used together.

Usually the ultraviolet-light absorbent may be used in an amount of1×10⁻⁴ to 2×10⁻³ mol/m², and preferably 5×10⁻⁴ to 1.5×10⁻³ mol/m². Anexcess amount of UV absorbent in some cases might cause in the unexposedpart (white background) of the color photographic material yellowing.

It will be preferable to apply the technical idea of enclosing the dyeimage with oxygen barrier layers made of a substance having a low oxygenpermeability (as disclosed in Japanese Patent Application (OPI) Nos.11330/1974 and 57223/1975) and the technical idea of providing a layerhaving an oxygen permeability of 20 ml/m².hr.atm or less under the colorimage forming layer (as disclosed in Japanese Patent Application (OPI)No. 85747/1981.)

In this invention, a variety of color couplers can be used. By "colorcoupler" is meant a compound that forms a dye upon coupling reactionwith an oxidation product of an aromatic primary amine developing agent.Useful color couplers are ones which form cyan, magenta, and yellow.Their typical examples include naphthol or phenol compounds, pyrazoloneor pyrazoloazole compounds, and open-chain or heterocyclic ketomethylenecompounds, respectively. Examples of the cyan, magenta, and yellowcouplers that can be used in this invention are disclosed in the patentscited in Research Disclosure (RD) 17643 (December 1978). ParagraphVIII-D, and 18717 (November 1979).

The magenta coupler that can be used in this invention includesoil-protected couplers of indazolone or cyanoacetyl type, preferably ofpyrazoloazole (e.g., pyrazotriazole) type. 5-pyrazolones substituted byan acyamino group at the 3-position are preferable in view of the hueand maximum densities of formed dyes and are disclosed in U.S. Pat. Nos.2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and3,936,015. Two-equivalent 5-pyrazolone couplers having as thecoupling-off group a nitrogen-linked coupling-off group (as disclosed inU.S. Pat. No. 4,310,619) or an arylthio group (as disclosed in U.S. Pat.No. 4,351,897) are preferable. A high image density can be obtained witha 5-pyrazolone coupler having the ballast group as disclosed in EuropeanPat. No. 73,636.

Examples of pyrazoloazole couplers include pyrazolobenzimidazoles (asdisclosed in U.S. Pat. No. 3,369,879), preferablypyrazole[5,1,-c][1,2,4]triazoles (as disclosed in U.S. Pat. No.3,725,067), pyrazolotetrazoles (as disclosed in Research Disclosure24220 (June 1984), and Pyrazolopyrazoles (as disclosed in ResearchDisclosure 24230 (June 1984). Imidazo[1,2,-b]pyrazoles andpyrazole-(1,5,-b)-(1,2,4)-triazole disclosed in European Pat. Nos.119,741 and 119,860, respectively are preferable since the formed dyehas reduced yellow side-absorption and superior fastness to light.

The cyan coupler that can be used in this invention includes naphtholcouplers and phenol couplers of oil-protected type. An example ofnaphthol coupler is that disclosed in U.S. Pat. No. 2,474,293 andpreferred examples of naphthol couplers are such two-equivalent naphtholcouplers as oxygen atom splitting-off type disclosed in U.S. Pat. Nos.4,052,212, 4,146,396, 4,228,233, and 4,296,200. Examples of the phenolcouplers are those disclosed in U.S. Pat. Nos. 2,369,929, 2,801,171,2,772,162, and 2,895,826.

Examples of cyan couplers stable to moisture and heat and advantageouslyused in this invention include phenol cyan couplers having a higheralkyl group than methyl group at meta position of the phenol nucleusdisclosed in U.S. Pat. No. 3,772,002 and phenol cyan couplers having aphenylureido group at 2-position and an acylamino group at 5-positiondisclosed in U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and4,427,767.

The effect of this invention will be advantageously achieved when atleast one of the compounds represented by formula (XII) or (XIII) belowis used as a cyan coupler. The compounds represented by formulas (XII)and (XIII) may be used together. ##STR21## wherein R₃₆, R₃₇, and R₃₉represent substituted or unsubstituted aliphatic, aromatic, orheterocyclic groups; R₃₈ and R₄₁ represent hydrogen atoms, halogenatoms, aliphatic groups, aromatic groups, or acylamino groups; R₃₈represents a group of nonmetallic atoms which forms, together with R₃₇,a nitrogen-containing 5- or 6-membered ring; R₄₀ represents an aliphaticgroup having at least 2 carbon atoms which may be further substituted;Y₃₁ and Y₃₂ represent hydrogen atoms or the groups that can besplitted-off upon oxidation coupling reaction with the developing agent;and n is 0 or 1. A dimeric or polymeric coupler may be formed throughone of the groups R₃₇, R₃₈, and Y₃₁, or one of the groups R₄₀, R₄₁, andY₃₂.

The term "aliphatic group" in this specification and claims meanslinear, branched, and cyclic aliphatic groups and also saturated andunsaturated aliphatic groups such as alkyl, alkenyl, and aralkyl groups.

The following is a detailed description of the cyan coupler representedby formula (XII) or (XIII).

R₃₆, R₃₇, and R₃₉ include, for example, a methyl group, butyl group,tridecyl group, cyclohexyl group, and allyl group, as aliphatic groupshaving 1 to 32 carbon atoms; phenyl a group and naphthyl group as arylgroups; and a 2-pyridyl group, 2-imidazolyl group, 2-furyl group, and6-quinolyl group as heterocyclic groups. These groups may be furthersubsituted with a group selected from alkyl groups, aryl groups,heterocyclic groups, alkoxyl groups (e.g., methoxy group and2-methoxyethoxy group), aryloxy groups (e.g., 2,4-di-tert-amylphenoxygroup, 2-chlorophenoxy group, and 4-cyanophenoxy group), alkenyloxygroups (e.g., 2-propenyloxy group), acyl groups (e.g., acetyl group andbenzoyl group), ester groups (e.g., butoxycarbonyl group,phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonylgroup, and toluenesulfonyloxy group), amido groups (e.g., acetylaminogroup, methanesulfonamide group, and dispropylsulfamoylamido group),carbamoyl groups (e.g., diemthylcarbamoyl group and ethylcarbamoylgroup), sulfamoyl groups (e.g., butylsulfamoyl group), imido groups(e.g., succinimido group and hydantoinyl group), ureido groups (e.g.,phenylureido group and dimethylureido group), aliphatic or aromaticsulfonyl groups (e.g., methanesulfonyl group and phenylsulfonyl group),aliphatic or aromatic thio groups (e.g., ethylthio group and phenylthiogroup), a hydroxyl group, cyano group, carboxyl group, nitro group,sulfo group, and halogn atoms.

In the case where R₃₈ in formula (XII) has an atom or group able to besubstituted with a substituent, it may be substituted by the substituentdescribed for R₆ above.

The aliphatic group represented by R₄₀ in formula (XIII) which has 2 ormore carbon atoms and may have a substituent group thereon includes, forexample, an ethyl group, propyl group, butyl group, pentadecyl group,tertbutyl group, cyclohexyl group, cyclohexylmethyl group,phenylthiomethyl group, dodecyloxyphenylthiomethyl group,butanamidomethyl group, and methoxymethyl group.

Y₃₁ and Y₃₂ in formulas (XII) and (XIII) represent hydrogen atoms orcoupling splitting-off groups (including coupling splitting-off atoms[the same shall apply hereinafter]). Their examples include halogenatoms (e.g., fluorine atom, chlorine atom, and bromine atom), alkoxylgroups (e.g., ethoxy group, dodecyloxy group,methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, andmethylsulfonylethoxy group), aryloxy groups (e.g., 4-chlorophenoxygroup, 4-methoxyphenoxy group, and 4-carboxyphenoxy group), acylozygroups (e.g., acetoxy group, tetradecanoyloxy group, and benzoyloxygroup), sulfonyloxy groups (e.g., methanesulfonyloxy group andtoluenesulfonyloxy group), amido groups (e.g., dichloroacetylaminogroup, heptafluorobutylamino group, methanesulfonylamino group, andtoluenesulfonylamino group), alkoxycarbonyloxy groups (e.g.,ethoxycarbonyloxy group and benzyloxycarbonyloxy group),aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy group), aliphatic oraromatic thio groups (e.g., ethylthio group, phenylthio group, andtetrazolylthio group), imido groups (e.g., succinimido group andhydantoinyl group), and aromatic azo groups (e.g., phenylazo groups).These splitting-off groups may contain a photographic useful group.

Among the cyan couplers represented by formula (XII) or (XIII) above thepreferable ones are as follows:

R₃₆ in formula (XII) is preferably an aryl group or heterocyclic group,and more preferably an aryl group further substituted by a halogen atom,alkyl group, alkoxyl group, aryloxy group, acylamino group, acyl group,carbamoyl group, sulfonamido group, sulfamoyl group, sulfonyl group,sulfamido group, oxycarbonyl group, or cyano group.

Where R₃₇ and R₃₈ in formula (XII) do not form a ring, preferably R₃₇ isa substituted or unsubstituted alkyl group or aryl group, and morepreferably an alkyl group substituted by a substituted arylozy group;and R₃₈ is preferably a hydrogen atom.

R₃₉ in formula (XIII) is preferably a substituted or unsubstituted alkylgroup or aryl group, and more preferably an alkyl group substituted by asubstituted aryloxy group.

R₄₀ in formula (XIII) is preferably an alkyl group having 2 to 15 carbonatoms or a methyl group having a substituent having 1 or more carbonatoms, the preferred substituent being an aryl group, alkylthio group,acylamino group, aryloxy group, and alkyloxy group.

R₄₀ in formula (XIII) is preferably an alkyl group having 2 to 15 carbonatoms, and more preferably an alkyl group having 2 to 4 carbon atoms.

R₄₁ in formula (XIII) is preferably a hydrogen atom or halogen atom, andmore preferably a chlorine atom or fluorine atom.

Y₃₁ and Y₃₂ in formulas (XII) and (XIII) are preferably a hydrogen atom,halogen atom, alkoxyl group, aryloxy group, acyloxy group, orsulfonamido group.

Y₃₂ i formula (XII) is preferably a halogen atom, and more preferably achlorine atom or fluorine atom.

Where n=0 in formula (XII), Y₃₁ is preferably a halogen atom, and morepreferably a chlorine atom or fluorine atom.

The following are the examples of cyan couplers represented by formulas(XII) and (XIII) above. They are illustrative only and should not beconstrued as restricting the scope of this invention. ##STR22##

Among the yellow couplers that can be used in this invention, thetypical examples are acylacetamide couplers of oil-protected type, whichare described in U.S. Pat. Nos. 2,407,210, 2,875,057, and 3,265,506.Two-equivalent yellow couplers are preferred in this invention. Theirexamples are yellow couplers of oxygen-atom linkage split-off typedisclosed in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,933,501, and4,022,620, and yellow couplers of nitrogen-atom linkage split-off typedisclosed in Japanese Patent Publication No. 10739/1983; U.S. Pat. Nos.4,401,752 and 4,326,024; Research Disclosure No. 18053 (April 1979);British Pat. No. 1,425,020; and West Germany Patent Application (OLS)Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812.

α-Pivaloylacetanilide couplers from dyes which are superior in fastnessespecially in fastness to light, and α-benzoylacetanilide couplersprovide high image density.

Preferable among the yellow couplers used in this invention are thosewhich are represented by formula (XIV) below. ##STR23## wherein R₄₂denotes a substituted or unsubstituted N-phenylcarbamoyl group; Z₁denotes a hydrogen atom or a group which is splitted-off upon couplingreaction with an oxidation product of the developing agent; and a dimeror polymer may be formed through Z₁.

The N-phenylcarbamoyl group R₄₂ in formula (XIV) above may have thesubstituent on the phenyl group selected from the group of substituentsacceptable for R₃₆ defined in formula (XII) above. Where there are twoor more substituents, they may be the same or different.

The preferred example of R₄₂ is represented by formula (XV) below.##STR24## wherein G₁ represents a halogen atom or alkoxyl group; G₂represents a hydrogen atom, halogen atom, or alkoxyl group which may hasa substituent; and R₄₃ denotes an alkyl group which may have asubstituent.

The substituents on G₂ and R₄₃ in formula (XV) are an alkyl group,alkoxyl group, aryl group, aryloxyl group, amino group, dialkylaminogroup, heterocyclic group, (e.g., N-morpholino group, N-piperidinogroup, and 2-furyl group), halogen atom, nitro group, hydroxyl group,carboxyl group, sulfo group, and alkoxycarbonyl group.

The couplers and other compounds and synthesis processes thereofillustrated in this invention are described in the followingliteratures. The cyan coupler compounds are described in U.S. Pat. Nos.2,772,162 and 4,333,999; Japanese Patent Application (OPI) No.98731/1983; and Japanese Patent Publication No. 11572/1974. The yellowcoupler compounds are described in Japanese Patent Application (OPI) No.48541/1979; Japanese Patent Publication No. 10739/1983; U.S. Pat. No.4,326,024; and Research Disclosure No. 18053. The couplers used in theExamples (mentioned later) of this invention can be prepared accordingto the synthesis method described in these literatures.

The above-mentioned coupler compound used in this invention may have theballast group described in Japanese Patent Application (OPI) No.42045/1983 and Japanese Patent Application Nos. 88940/1983, 52923/1983,52924/1983, and 52927/1983.

The cyan coupler used in this invention shows improved preservability offormed dye images (especially cyan images), particularly fastness tolight, when used in combination with an ultraviolet-light absorbentrepresented by formula (XI). The cyan coupler may be coemulsified withthis ultraviolet-light absorbent.

In this invention, a known discoloration inhibitor used for the magentacoupler as mentioned above may be used for the improvement of thefastness of the cyan image or yellow image.

Preferable among these known discoloration inhibitors are those whichare represented by formulas (XVI) and (XVII) below. ##STR25## whereinR₄₄ represents a hydrogen atom, aliphatic group, aromatic group,heterocyclic group, or substituted silyl group ##STR26## wherein R₅₄,R₅₅, and R₅₆, which are the same or different, each represents aliphaticgroups, aromatic groups, aliphatic oxy groups, or aromatic oxy groups.These groups may have the substituents acceptable for R₃₆ in formula(XII). R₄₅, R₄₆, R₄₇, R₄₈, and R₄₉ may be the same or different, eachdenoting a hydrogen atom, alkyl group, aryl group, alkoxyl group,hydroxyl group, mono- or dialkylamino group, imino group, and acylaminogroup. R₄₄ and R₄₅ may combine with each other to form a 5- or6-membered ring. R₅₀, R₅₁, R₅₂, and R₅₃ may be the same or different,each denoting a hydrogen atom and alkyl group. X₀ denotes a hydrogenatom, aliphatic group, acyl group, aliphatic or aromatic sulfonyl group,aliphatic or aromatic sulfinyl group, oxyradical group, and hydroxylgroup. A₀ denotes a group of non metallic atoms necessary to form a 5-,6-, or 7-membered ring.

The following are the typical examples of the discoloration inhibitor.##STR27##

The compounds represented by formulas (XVI) and (XVII) may be used incombination with one another, and may also be used in combination with aknown discoloration inhibitor.

The processes for synthesizing the compounds represented by formulas(XVI) and (XVII) and other compounds than the typical examples givenabove are disclosed in British Pat. Nos. 1,326,889, 1,354,313, and1,410,846; U.S. Pat. Nos. 3,336,135 and 4,268,593; Japanese PatentPublication Nos. 1420/1976 and 6623/1977; and Japanese PatentApplication (OPI) Nos. 114036/1983 and 5246/1984.

The compound represented by formula (XVI) or (XVII) is used in an amountof 0.5 to 200 wt%, preferably 2 to 150 wt% based on the yellow coupleror cyan coupler. The amount varies depending on the type of yellowcoupler or cyan coupler to be used. It is preferably coemulsified with ayellow coupler or cyan coupler.

The couplers in this invention may be used in various manners accordingto the characteristic properties required. For example, two or morekinds of couplers may be incorporated in the same photosensitive layer,or the same coupler may be incorporated in two or more layers.

The coupler discoloration inhibitor and ultraviolet-light absorbent usedin this invention may be incorporated into the photosensitive materialby the known dispersing methods. Typical examples include soliddispersion method, alkali dispersion method, preferably latex dispersionmethod, and more preferably oil-in-water dispersion method. According tothe oil-in-water dispersion method, they are dissolved in a high-boilingorganic solvent (bp. 175° C. or more) or a low-boiling auxiliary solventor a mixture thereof, and the resulting solution is finely dispersed inwater or an aqueous solution of gelatin in the presence of a surfaceactive agent. Examples of the high-boiling organic solvent are describedin U.S. Pat. No. 2,322,027. For dispersing phase reversal of emulsioncan be utilized. If necessary, prior to coating, the auxiliary solventmay be removed or reduced by distillation, "noodle" washing, orultrafiltration.

Examples of the high-boiling organic solvents include phthalic esters(dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,and decyl phthalate, etc.), phosphoric or phosphonic esters (triphenylphosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate,tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate,tributoxyethyl phosphate, trichloropropylphosphate,di-2-ethylhexylphenyl phosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxy benzoate, etc.),amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols orphenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphaticcarboxylic esters (dioctylazelate, glycerol tributyrate, isostearyllactate, trioctyl citrate, etc.), aniline derivatives(N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), and hydrocarbons(paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). The auxiliarysolvents are organic solvents having a boiling point higher than about30° C., preferably from about 50° C. to about 160° C. Examples of thesesolvents include ethyl acetate, butyl acetate, ethyl propionate, methylethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide,etc.

The steps and effect of the latex dispersion method and the examples oflatex for impregnation are described in U.S. Pat. No. 4,199,363, andWest Germany Application (OLS) Nos. 2,541,274 and 2,541,230.

Usually the color couplers are used in an amount of 0.001 to 1 mol per 1mol of photosensitive silver halides. The preferred amount of coupler is0.01 to 0.5 mol for yellow coupler, 0.003 to 0.3 mol for magentacoupler, and 0.002 to 0.3 mol for cyan coupler.

According to this invention, the color photographic material may includea special coupler as required in addition to the yellow, magenta, andcyan couplers represented by the formulas given above. For example, itis preferable to use a colored coupler for the picture-taking colorphotosensitive material in order to correct the unwanted absorption ofshort wave light atributable to the dyes formed from the magenta andcyan couplers. Examples of such colored coupler include yellow-coloredmagenta coupler described in U.S. Pat. No. 4,163,670 and Japanese PatentPublication No. 39413/1982, and magenta-colored cyan coupler describedin U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Pat. No.1,146,368.

The color couplers in the photosensitive material is preferably renderednondiffusing by the incorporation of a ballast group or by thepolymerization. It is possible to reduce the amount of silver coated andto obtain a higher sensitivity with a two-equivalent color coupler inwhich the hydrogen atoms at the coupling active positions aresubstituted by coupling split-off groups, than with a four-equivalentcolor coupler in which the coupling active positions are occupied byhydrogen atoms. It is also possible to use a coupler that forms a dyehaving a proper degree of diffusion, a colorless coupler, a DIR couplerthat releases a development inhibitor upon coupling reaction, or acoupler that releases a development accelerator.

It is possible to improve the grainness by using the color couplers incombination with a coupler which forms a dye having a proper degree ofdiffusion. Such type of magenta coupler is disclosed in U.S. Pat. No.4,366,237 and British Pat. No. 2,125,570; and such type of yellow,magenta, or cyan coupler is disclosed in European Pat. No. 96,570 andWest Germany Patent Application (OLS) No. 3,234,533.

Examples of the polymerized dye-forming couplers are disclosed in U.S.Pat. Nos. 3,451,820 and 4,080,211. Examples of polymerized magentacouplers are disclosed in British Pat. No. 2,102,173 and U.S. Pat. No.4,367,282.

The silver halide emulsion used in this invention is usually produced bymixing a solution of water-soluble silver salt (e.g., silver nitrate)and a solution of water-soluble halide (e.g., potassium bromide, sodiumchloride, or potassium iodide, or a mixture thereof) in the presence ofa solution of water-soluble polymer such as gelatin.

Other examples of the silver halides include mixed silver halides suchas silver chlorobromide, silver chloroiodobromide, and silveriodobromide. The silver halide which is advantageously used in thisinvention is silver chloroiodobromide, silver chlorobromide, or silveriodobromide which contains no or less than 3 mol% of silver iodide.

The silver halide crystals may have such structure that the internalphase differs from the surface phase, or the entire crystals have auniform phase or polyphase having joining structure or a mixturethereof. In the case of silver chlorobromide crystals having differentphases, each crystal may have a nucleus or a single layer or a pluralityof layers richer with silver bromide or silver chloride than the averagesilver halide composition. In other words, the crystals may be coveredwith a layer richer with silver bromide or silver chloride than theaverage silver halide composition. The average crystal size of silverhalides should preferably be from 0.1 μm to 2 μm, and more preferablyfrom 0.15 μm to 1 μm. For spherical crystals or nearly sphericalcrystals, the diameter is regarded as the crystal size, and for cubiccrystals, the edge length is regarded as the crystal size. The averageis obtained from their projected area.

The crystal size-distribution may be either narrow or broad. Theemulsion that can be used in this invention may contain monodispersesilver halide crystals having such a narrow size-distribution thatcrystals having the average size plus and minus 40% account for morethan 90%, especially more than 95% by number or weight of crystals. Inorder to produce the desired gradation, it is possible to coat two ormore emulsions each containing monodisperse silver halide crystals ofdifferent size, in the form of a uniformly mixed layer or individualmultiple layers. (In this case, the emulsions have substantially thesame color sensitivity.) Alternatively, it is also possible to coat twoor more emulsions each containing polydisperse silver halide crystals ora mixture of monodisperse silver halide crystals and polydisperse silverhalide crystals, in the form of a mixed layer or multiple layers.

The emulsion used in this invention may contain silver halide crystalshaving the regular crystal structure such as cube, octahedron,dodecahedron, and tetradecahedron, or irregular crystal structure suchas a spherical structure or the combination thereof. In addition, theemulsion may contain tabular grains having a diameter-to-thickness ratioof 5 or more, especially greater than 8, which account for more 50% ofthe total projected area of crystals. Moreover, the emulsion may containa mixture of crystals of different types. The emulsion may be of thesurface latent image type or the internal latent image type, the formerforming the latent image on the surface of grains and the latter formingthe latent image inside grains.

The photographic emulsion used in this invention can be preparedaccording to the processes described in P. Glafkides, Chimie et PhysiquePhotographique (Pallmontel, 1967) G. F. Guffin, Photographic EmulsionChemistry (Focal Press, 1966), and V. L. Zelikman, Making and CoatingPhotographic Emulsion (Focal Press, 1964). Any of an acidic process, aneutral process or an ammoniacal process can be used. As a manner ofreacting a soluble silver salt with a soluble halide salt, any of thesingle jet method, double jet method and a combination thereof may beemployed.

A process of forming grains in the presence of excess silver ion (theso-called reversal mixing process) can be employed as well. As one typeof the double jet method, the "controlled double jet" process can beemployed wherein the pAg in the liquid phase of silver halide formationis kept constant. This process provides a silver halide emulsioncontaining regular silver halide grains having an approximatelymonodisperse particle size.

During formation or physical ripening of the silver halide grains,cadmium salts, zinc salts, lead salts, thallium salts, iridium salts orthe complex salts thereof, rhodium salts or the complex salts thereof,iron salts or the complex salts thereof, etc., may also be present.After physical ripening, silver halide emulsions are usually subjectedto desalting and chemical sensitization for use in coating.

Physical ripening in the presence of silver halide solvents, e.g.,ammonia, potassium thiocyanate, thioethers and thiones described in U.S.Pat. No. 3,271,157, Japanese Patent Application (OPI) Nos. 12360/1976,82408/1978, 144319/1978, 100717/1979 and 155828/1979 provides silverhalide emulsions having regular crystal forms and monodisperse grainsize distribution. Removing soluble salts from emulsions before andafter physical ripening can be achieved by noodle washing, flocculationprecipitation or ultra-filtration, etc.

The silver halide emulsion for the present invention may be subjected tochemical sensitization; sulfur or selen sensitization, reductionsensitization and noble metal sensitization can be employed alone or incombination thereof.

Sulfur sensitization using active gelatine or sulfur-containingcompounds capable reacting with silver (e.g., thiosulfates, thioureas,mercapto compounds, rhodanines, etc.); reduction sensitization using areductive substance (e.g., stannous salts, hydrazine derivatives,formamidinesulfinic acid, silane compounds, etc.); and noble metalsensitization using noble metal compounds (e.g., complex salts of theGroup VIII metals such as Pt, Ir, Pd, Rh, Fe, etc., as well as goldcomplex salts) can be employed alone or in combination.

Photographic emulsions in the present invention can be spectrallysensitized with photographic sensitizing dyes. Useful dyes includecyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolarcyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.Particularly useful dyes are cyanine dyes, merocyanine dyes and complexmerocyanine dyes.

These dyes may have any of the following basic heterocyclic nuclei whichare commonly used for cyanine dyes. Pyrroline nucleus, oxazolinenucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazolenucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, andpyridine nucleus. Those nuclei formed by condensation of theabove-mentioned nuclei with an aliphatic hydrocarbon ring or aromatichydrocarbon ring, such as indolenine nucleus, benzindolenine nucleus,indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus,benzimidazole nucleus, naphthoimidazole nucleus, quinoline nucleus, andimidazo-(4,5,-b)-quinoquizaline nucleus. These nuclei may be substitutedon the carbon atom.

The merocyanine dye or compound merocyanine dye may have, as a nucleushaving the ketomethylene structure, a 5- or 6-membered hetero ringnucleus such as pyrazolin-5-on nucleus, thiohydantoin nucleus,2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus,rhodanine nucleus, thiobarbituric acid, 2-thioselenazolidine-2,4-dionenucleus, pyrazolo[1,5-a]benzimidazole, and pyrazolo[5,1-b]quinazolonenucleus.

These sensitizing dyes may be used alone or in combination. Acombination of sensitizing dyes is often employed particularly for thepurpose of supersensitization.

Together with the sensitizing dye, a supersensitizing substance such asa dye which itself is not sensitizing or a substance which substantiallydoes not absorb visible light may be incorporated in the emulsion. Forexample, aminostilbene compounds substituted with a nitrogen-containinghetero ring (for example, those described U.S. Pat. Nos. 2,933,390 and3,635,721), aromatic acid-formaldehyde condensates (for example, thosedescribed in U.S. Pat. No. 3,743,510), cadmium salts, azaindenecompounds, etc., may be incorporated. The combinations described in U.S.Pat. Nos. 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularlyuseful.

To the photographic emulsion for use in the present invention, variouscompounds can be incorporated for the purpose of stabilizingphotographic properties and of preventing fog formation during the stepsof producing, storing or processing of, photographic materials. Manycompounds known as antifoggants or stabilizers can be added; typicalexamples include azoles, e.g., benzothiazolium salts, benzimidazoliumsalts, imidazoles, benzimidazoles (preferably 5-nitrobenzimidazole),nitroindazoles, benzotriazoles (preferably 5-methylbenzotriazoles), andtriazoles; mercapto compounds (e.g., mercaptothiazoles,mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptobenzoxazoles,mercaptooxadiazoles, mercaptothiadiazoles, mercaptotriazoles,mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole),mercaptopyrimidines, and mercaptotriazines; thiocarbonyl compounds(e.g., oxazolinethione); azaindenes (e.g., triazaindenes,tetraazaindenes (particularly4-hydroxy-6-methyl-(1,3,3a,7)-tetraazaindene), and pentaazaindenes);benzenethiosulfonic acids; benzenethiosulfinic acids; benzenesulfonamideand purines (e.g., adenine).

Detailed description about the antifoggants and stabilizers will befound in U.S. Pat. Nos. 3,954,474 and 3,982,947; Japanese PatentPublication No. 28660/1977; Research Disclosure 17643 (December 1978)VIA-VIM; and E. J. Birr, Stabilization of Photographic Silver HalideEmulsions (Focal Press, 1974).

The photosensitive material of this invention may contain, as a colorantifoggant or discoloration inhibitor, a hydroquinone derivative,aminophenol derivative, amine, gallic acid derivative, catecholderivative, ascorbic acid derivative, colorless coupler, orsulfoneamidephenol derivative.

The photographic material of this invention may have in the photographicemulsion layers and other hydrophilic colloid layers a brightening agentderived from stilbene, triazine, oxazole, or coumarin. It may bewater-soluble but may be in the form of dispersion when water insoluble.Examples of the fluorescent brightener are described in U.S. Pat. Nos.2,632,701, 3,269,840, and 3,359,102; British Pat. Nos. 852,075 and1,319,763; and Research Disclosure Vol. 176, 17643 (issued December1978), page 24, lines 9 to 36 in the left column.

In the case where the photosensitive material of this invention has inthe hydrophilic colloid layers a dye and ultraviolet light absorbent,they may be mordanted by a cationic polymer. Examples of such a polymerare disclosed in British Pat. No. 685,475; U.S. Pat. Nos. 2,675,316,2,839,401, 2,882,156, 3,048,487, 3,184,309, and 3,445,231; West GermanyPatent Application (OLS) No. 1,914,362; and Japanese Patent Application(OPI) Nos. 47624/1975 and 71332/1975.

The photosensitive material of this invention may contain, as a colorantifoggant, a hydroquinone derivative, aminophenol derivative, gallicacid derivative, or ascorbic acid derivative. Examples of the colorantifoggant are described in U.S. Pat. Nos. 2,360,290, 2,336,327,2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659,2,732,300, and 2,735,765; Japanese Patent Application (OPI) Nos.92988/1975, 92989/1975, 93928/1975, 110337/1975, and 146235/1977; andJapanese Patent Publication No. 23813/1975.

The photosensitive material of this invention may contain awater-soluble dye in the hydrophilic colloid layers as a filter dye orfor the prevention of irradiation and halation and for other purpose.Examples of such a dye are oxonol dyes, styryl dyes, merocyanine dyes,anthraquinone dyes, and azo dyes. Cyanine dyes, azomethine dyes,triarylmethane dyes, and phthalocyanine dyes may be used. It is alsopossible to add an oil-soluble dye to the hydrophilic colloid layer tobe emulsified by the oil-in-water dispersion method.

The emulsion layers and intermediate layers of the photosensitivematerial of this invention are combined with gelatin or otherhydrophilic colloid as the binding material and protective colloid.Examples of such gelatin or hydrophilic colloid are a gelatinderivative, graft polymer of gelatin and other polymer, protein such asalbumin and casein, cellulose derivative such as hydroxyethyl cellulose,carboxymethyl cellulose, and cellulose sulfate ester, sodium alginate,sugar derivative such as starch derivative, and hydrophilic syntheticpolymeric substance (homopolymer or copolymer) such as polyvinylalcohol, polyvinyl alcohol having partial acetal groups,poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,polyacrylamide, polyvinyl imidazole, and polyvinyl pyrazole.

The gelatin may be the commercially available lime-treated gelatin oracid-treated gelatin, or enzyme-treated gelatin as disclosed in Bulletinof the Society of Scientific Photography of Japan, No. 16, p. 30 (1966).The decomposition product of gelatin formed by hydrolysis or enzymicaction may be used.

The photosensitive material of this invention may contain an inorganicor organic hardening agent in the photosensitive layers or anyhydrophilic colloid layer forming the backing layer.

The photosensitive material of this invention may contain a coatingauxiliary and one or more surfactants for the improvement of antistaticproperties, slip properties, emulsification and dispersion, antiblockproperties, and other photographic properties (e.g., acceleration ofdevelopment, high contrast, and sensitization).

The photosensitive material of this invention may be incorporated with,in addition to the above-mentioned additives, a variety of stabilizer,stain inhibitor, developing agent or precursor thereof, developmentaccelerator or precursor thereof, slip agent, mordant, matting agent,antistatic agent, plasticizer, and other additives useful for thephotosensitive material. Examples of the additives are described inResearch Disclosure 17643 (December 1978) and 18716 (November 1979).

This invention can be applied to the multilayer-multicolor photographicmaterial having at least two layers of different spectral sensitivitydeposited on a film support. The multilayer color photographic materialusually has at least a red-sensitive emulsion layer, a green-sensitiveemulsion layer, and a blue-sensitive emulsion layer deposited on filmsupport, respectively. The other of these layer may be selected asdesired. The preferred order is red-sensitive, green-sensitive, andblue-sensitive starting from the support, or blue-sensitive,red-sensitive, and green-sensitive starting from the support. Eachemulsion layer may be composed of two or more emulsion layers ofdifferent sensitivity, or may be composed of two or more emulsion layersof the same sensitivity with a non-sensitive layer interposedtherebetween. Usually, the red-sensitive emulsion layer contains acyan-forming coupler, the green-sensitive emulsion layer contains amagenta-forming coupler, and the blue-sensitive emulsion layer containsa yellow-forming coupler. This combination may be different in somecases.

The photosensitive material of this invention preferably includes, inaddition to the silver halide emulsion layers, auxiliary layers such assubbing layer, protective layer, intermediate layer, filter layer,antihalation layer, and backing layer. Moreover, if necessary, a secondUV light absorbing layer may be provided between the red-sensitiveemulsion layer and the green-sensitive emulsion layer. This UV lightabsorbing layer preferably contain the UV light absorber described aboveor any other known UV light absorber.

In the photosensitive material of this invention, the photographicemulsion layer and other layers are coated on a flexible support such asplastic film, paper, and cloth, or a rigid support such as glass,porcelain, and metal, which are commonly used for photosensitivematerials. An example of the flexible support is a film ofsemi-synthetic or synthetic polymer such as cellulose nitrate, celluloseacetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride,polyethylene terephthalate, and polycarbonate, and paper coated orlaminated with baryta layer or α-olefin polymer (e.g., polyethylene,polypropylene, and ethylene/butene copolymer). The support may becolored by using a dye or pigment, or may be black in color for lightshielding. The support is usually applied an undercoating for theimproved bonding with the photographic emulsion layers. Prior to orafter the undercoating, the surface of the support may be subjected toglow discharge, corona discharge, UV light irradiation, or flametreatment.

The coating of the photographic emulsion layers and other hydrophiliccolloid layers may be conducted by the known manners such as dipcoating, roller coating, curtain coating, and extrusion coating. Ifnecessary, a multiplicity of layers may be coated at one time by themethod disclosed in U.S. Pat. Nos. 2,681,294, 2,761,791, 3,526,528, and3,508,947.

For color development processing of the photosensitive material of thisinvention, it is desirable to use an alkaline aqueous solution composedmainly of a color developing agent of aromatic primary amine type. Asthe color developing agent, an aminophenol compound may be used, but theuse of a p-phenylenediamine compound is preferable. Examples of such acompound are 3-methyl-4-amino-N,N-diethylaniline,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline, and3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, sulfates thereof,hydrochlorides thereof, and p-toluenesulfonates thereof. The amines areused in the form of salts, because they are stable rather than the freeform.

The color developing solution generally contains a pH buffer such asalkali metal carbonate, borate, and phosphate; a development retardersuch as bromide, iodide, benzimidazole, benzothiazole, and mercaptocompound; and an antifoggant. In addition, the color developing solutionmay be incorporated, as required, with a preservative such ashydroxylamine and sulfite; an organic solvent such as triethanolamineand ethylene glycol; a development accelerator such as benzyl alcohol,polyethylene glycol, quaternary ammonium salt, and amine; dye formingcouplers and competitive couplers; a nucleating agent such as sodiumboron hydride; an auxiliary developing agent such as1-phenyl-3-pyrazolidone; a thickening agent; a chelating agent such asamino polycarboxylic acid, amino polysulfonic acid, alkylsulfonic acid,and phosphonocarboxylic acid; and an antioxidant as disclosed in WestGermany Patent Application (OLS) No. 2,622,950.

In the development processing of color reversal material, black andwhite development is usually performed prior to color development. Forthe black and white developing solution, it is possible to use any knownblack and white developing agent such as dihydroxybenzenes (e.g.,hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), andaminophenols (e.g., N-methyl-p-aminophenol), individually or incombination with one another.

After color development, the photographic emulsion layer usually undergobleaching treatment. The bleaching may be performed simultaneously withor separately from fixing treatment. The bleaching agent includescompounds of polyvalent metal such as iron (III), cobalt (III), chromium(VI), and copper (II), peracids, quinones, and nitron compounds.Examples of the bleaching agent are ferricyanides, dichromates, organiccomplex salts of iron (III) or cobalt (III) (e.g., complex salts ofaminopolycarboxylic acid such as ethylenediaminetetraacetic acid,ethylenetriaminepentaacetic acid, nitrilotriacetic acid, and1,3-diamino-2-propanoltetraacetic acid; and complex salts of organicacid such as citric acid, tartaric acid, and malic acid), persulfates,manganates, and nitrosophenol. Iron (III) ethylenediaminetetraacetateand persulfates are preferable among them in view of rapid treatment andenvironmental pollution. Especially, iron (III)ethylenediaminetetraacetate is useful for the independent bleachingsolution as well as the combined developing and fixing bath.

The bleaching bath or the bleach-fix bath may be incorporated with avariety of accelerators as required. Examples of the bleach acceleratorsare bromine ions and iodine ions; thiourea compounds as disclosed inU.S. Pat. No. 3,706,561, Japanese Patent Publication Nos. 8506/1970 and26586/1974, and Japanese Patent Application (OPI) Nos. 32735/1978,36233/1978, and 37016/1978; thiol compounds as disclosed in JapanesePatent Application (OPI) Nos. 124424/1978, 95631/1878, 57831/1978,32736/1978, 65732/1978, and 52534/1979, and U.S. Pat. No. 3,893,858;heterocyclic compounds as disclosed in Japanese Patent Application (OPI)Nos. 59644/1974, 140129/1975, 28426/1978, 141623/1978, 104232/1978, and35727/1979; thioether compounds as disclosed in Japanese PatentApplication (OPI) Nos. 20832/1977, 25064/1980, and 26506/1980; tertiaryamines as disclosed in Japanese Patent Application (OPI) No. 84440/1973;and thiocarbamoyls as disclosed in Japanese Patent Application (OPI) No.42349/1974. They may be used individually or in combination with oneanother. Among the bleach accelerators identified above, bromine ions,iodine ions, thiol compounds, and disulfide compounds are particularlyuseful. They are effective when used for bleach-fix of thepicture-taking color photosensitive material.

The fixing agent is a thiosulfate, thiocyanate, thioether compound,thiourea, and iodide. A thiosulfate is preferable. The bleach-fix bathor the fixing bath is preferably incorporated with a preservative suchas sulfite, bisulfite, and carbonyl-bisulfite adduct.

Bleach-fix or fixing is usually followed by washing. Water for washingmay be incorporated with a variety of known compounds for the preventionof precipitation and the saving of water. For example, a water softenersuch as inorganic phosphoric acid, aminopolycarboxylic acid, and organicphosphoric acid may be added for the prevention of precipitation; and anantiseptic may be added for the inhibition of bacteria, algae, andmolds. Other additives that may be added as required include a hardeningagent such as magnesium salt and aluminum salt and a surface activeagent that makes for uniform drying. A compound as disclosed in Phot.Sci, Eng., Vol. 6 (1965), p. 344-359, Water Quality Criteria, by L. E.West may be used as an additive. The addition of a chelating agent andantiseptic agent is paticularly effective.

The developed dyes are deteriorated by light and heat and alsodiscolored by molds during storage. In particular, cyan photographicimages are easily vulnerable by molds. Thus, it is desirable to use amold protecting agent such as 2-thiazolylbenzimidazole as disclosed inJapanese Patent Application (OPI) No. 157244/1982. The mold protectingagent may be incorporated into the photosensitive material or may beadded to the development process. In other words, it may be added in anystep so long as it remains in the processed photosensitive material.

The washing is usually performed in the counter-current manner using twoor more vessels for the saving of water. The washing step may bereplaced by the multistage countercurrent stabilizing step as disclosedin Japanese Patent Application (OPI) No. 8543/1982. This step requires 2to 9 countercurrent baths incorporated with a variety of compounds forthe stabilization of photographic images. Examples of the additives areformalin and buffers to adjust the pH of the gelatin emulsion. (Thebuffers are prepared by combining boric acid, metaboric acid, borax,phosphate, carbonate, potassium hydroxide, ammonia water, monocarboxylicacid, dicarboxylic acid, polycarboxylic acid, etc. with one another.)Other additives are water softener (e.g., inorganic phosphoric acid,aminopolycarboxylic acid, organic phosphoric acid, aminopolysulfonicacid, and phosphonocarboxylic acid), antiseptic agent (e.g.,benzoisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole, andhalogenated phenol), surface active agent, fluorescent brightener, andhardening agent. Two or more additives for the same object may be usedtogether.

In order to adjust the pH of the emulsion after processing, it ispreferable to add an ammonium salt such as ammonium chloride, ammoniumnitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, andammonium thiosulfate.

The silver halide color photosensitive material of this invention may beincorporated with precursors of color developing agents so as tosimplify and speed up the processing. Examples of such precursors areindoaniline compounds (as disclosed in U.S. Pat. No. 3,342,597), Schiffbase compounds (as disclosed in U.S. Pat. No. 3,342,599 and ResearchDisclosure Nos. 14850 and 15159), aldol compounds (as disclosed inResearch Disclosure No. 13924), metal salt complexes (as disclosed inU.S. Pat. No. 3,719,492), urethane compounds (as disclosed in JapanesePatent Application (OPI) No. 135628/1978), and salt type precursors (asdisclosed in Japanese Patent Application (OPI) Nos. 6235/1981,16133/1981, 59232/1981, 67842/1981, 83734/1981, 83735/1981, 83736/1981,89735/1981, 81837/1981, 54430/1981, 106241/1981, 107236/1981,97531/1982, and 83565/1982).

The silver halide color photosensitive material of this invention may beincorporated with a 1-phenyl-3-pyrazolidone as required so as toaccelerate color development. Examples of such a compound are disclosedin Japanese Patent Application (OPI) Nos. 64339/1981, 144547/1982,211147/1982, 50532/1983, 50536/1983, 50533/1983, 50534/1983, 50535/1983,and 115438/1983.

The processing solutions for the photosensitive material of thisinvention is used at 10° C. to 50° C., although the standard temperatureis 33° C. to 38° C. The temperature may be raised to accelerateprocessing and to reduce the processing time. To the contrary, thetemperature may be lowered to improve the photographic image quality andthe stability of the processing solutions. For the saving of silver inthe photosensitive material, the processing may be intensified by usingcobalt or hydrogen peroxide as disclosed in West Germany Pat. No.2,226,770 and U.S. Pat. No. 3,674,499.

The processing baths may be provided with a heater, temperature sensor,level sensor, circulating pump, filter, floating lid, squeezer, and thelike, as required.

In the present invention, the silver halide color photosensitivematerial is formed by combining a specific magenta coupler and chromanderivative together. Therefore, it is greatly improved in thepreservation of quality of photographic image. In addition, it is freefrom discoloration and fogging and keeps the photographic color imagewithout decreasing the color density. Furthermore, white backgroundportions of the photosensitive material do not create the yellow stainsby light, heat, and moisture after the development processing anddiscoloration is minimized over the entire density range of photographiccolor images and there is no change in color balance.

It is to be understood that the 6-hydroxy-2,4,4,7-tetramethylchromanderivative of this invention produces a strong antioxidant action, andit is useful as an antioxidizing agent for synthetic polymeric productsand petroleum products such as dyes, rubbers, and plastics. It is alsoeffective in preventing the discoloration of color photographic imagesformed by the subtractive color process.

The invention is now described in more detail with reference to thefollowing examples. Examples 1 to 3 are directed to the syntheses of2-(2-alkoxy-5-hydroxy-4-methylphenyl)-6-hydroxy-2,4,4,7-tetramethylchromanderivatives as shown in the synthesis scheme (1). Example 4 is directedto the syntheses of2-(5-alkoxy-2-hydroxy-4-methylphenyl)-6-hydroxychroman derivatives asshown in the synthesis scheme (2). Examples 5 to 13 are directed to theapplication of the 6-hydroxy-2,4,4,7-tetramethylchroman as anantioxidant.

EXAMPLE 1 (1) Synthesis of compound 2

50 g (0.152 mol) of compound 1 was heated with 50 ml of toluene and 43ml (0.456 mol) of acetic anhydride under reflux for 6 hours. Thereaction solution was evaporated to dryness under reduced pressure. 12.5ml of isopropanol and 112.5 ml of n-hexane were added forcrystallization. On filtration of crystals, there was obtained 57.8 g ofcompound 2.

Yield: 92%, m.p. 163° C.

(2) Synthesis of exemplified compound (3)

To 41.2 g (0.10 mol) of compound 2 were added 80 ml ofdimethyl-formamide, 29.9 g (0.12 mol) of dodecyl bromide, and 16.5 g(0.12 mol) of anhydrous potassium carbonate, followed by stirring at 70°C. for 8 hours. While the reaction solution was kept at 25° C., therewas added a solution of 16.5 g (0.30 mol) of potassium hydroxide in 165ml of methanol, followed by stirring for 30 minutes. Solids were removedby filtration, and the filtrate was poured into ice-cooled acid water(with hydrochloric acid) for neutralization, followed by extraction with300 ml of ethyl acetate. After thorough washing with water, the ethylacetate was distilled away under reduced pressure, and 125 ml ofn-hexane was added for crystallization. The crystals were filtered offand then recrystallized from acetonitrile. Thus there was obtained 38.7g of the exemplified compound (3) in the form of colorless crystals.

Yield: 78%, m.p. 166°-167° F.

IR (KBr, cm⁻¹): 3255, 1505, 1195, 1170, 883, 870.

NMR (CDCl₃, δ): 6.79 (1H, s), 6.73 (1H, s), 6.56 (2H, s), 4.58 (1H, s),4.48 (1H, s), 3.91 (2H, t, J=6.7 Hz), 2.92 (1H, d, J=15 Hz), 2.13 (3H,s), 1.91 (1H, d, J=15 Hz), 1.63 (3H, s), 1.9-1.1 (20H, m), 1.19 (3H, s),0.88 (3H, t, J=6 Hz), 0.80 (3H, s).

M/S (m/e): 496 (M⁺)

Elemental analysis (C₃₂ H₄₈ O₄). Found: C: 77.26%; H: 9.87%; Calcd: C:77.38%; H: 9.74%.

EXAMPLE 2 Synthesis of exemplified compound (A-8)

To 41.2 g (0.10 mol) of compound 2 was added 150 ml of dimethylacetamide for dissolution. While this solution was kept at 5° to 10° C.,4.8 g (0.12 mol) of sodium hydride (60% dispersion in oil) was addedwith stirring. Then 19.7 g (0.12 mol) of hexyloxyethylene chloride wasadded over 15 minutes, followed by stirring at 27° to 29° C. for 4hours. 20 ml of methanol was added and then there was added a solutionof 16.5 g (0.30 mol) of potassium hydroxide in 165 ml of methanol,followed by stirring for 30 minutes. The reaction solution was pouredinto ice-cooled acid water (with hydrochloric acid) for neutralization,followed by extraction with 300 ml of ethyl acetate. After thoroughwater washing, the ethyl acetate was distilled away under reducedpressure, and 125 ml of n-hexane was added for crystallization. Thecrystals were filtered off and then recrystallized from 100 ml ofacetonitrile. Thus there was obtained 31.6 g of the exemplified compound(A-8) in the form of colorless crystals.

Yield: 69%, m.p. 198°-199° C.

IR (KBr, cm⁻¹): 3100, 1500, 1195, 1170, 883, 870.

NMR (CDCl₃ /DMSO-d₆, δ): 7.95 (1H, broad s), 7.82 (1H, broad s), 6.82(1H, s), 6.71 (1H, s), 6.58 (1H, s), 6.55 (1H, s), 4.15-3.95 (2H, m),3.90-3.70 (2H, m), 3.53 (2H, t, J=6.7 Hz), 2.99 (1H, d, J=15 Hz), 2.16(3H, s), 2.10 (3H, s), 1.85 (1H, d, J=15 Hz), 1.62 (3H, s), 1.8-1.1 (8H,m), 1.20 (3H, s), 0.88 (3H, m), 0.70 (3H, s).

M/S (m/e): 457 (M⁺)

Elemental analysis (C₂₈ H₄₀ O₅). Found: C: 73.37%; H: 9.08%; Calcd: C:73.49%; H: 9.03%.

EXAMPLE 3 Synthesis of exemplified compound (A-7)

To 41.2 g (0.10 mol) of compound 2 was added 150 ml of dimethylacetamide for dissolution. While this solution was kept at 5° to 10° C.,4.8 g (0.12 mol) of sodium hydride (60% dispersion in oil) was addedwith stirring. Then 30.7 g (0.11 mol) of 2-bromodecanoic acid was addedover 15 minutes, followed by stirring at 27° to 30° C. for 5 hours. Thereaction solution was cooled to 5°-10° C., and 20 ml of methanol wasadded. The reaction solution was poured into ice-cooled acid water (withhydrochloric acid) for neutralization, followed by extraction with 300ml of ethyl acetate. After thorough water washing, the ethyl acetate wasdried over sodium sulfate. The sodium sulfate was filtered off and thesolvent was distilled away. To the residues were added 150 ml of ethanoland 41.4 g (0.30 mol) of anhydrous potassium carbonate, followed bystirring at 27°-30° C. for 1 hour. Solids were filtered off and thefiltrate was poured into ice-cooled acid water (with hydrochloric acid)for neutralization, followed by extraction with 300 ml of ethyl acetate.The organic layer was thoroughly washed with water and then dried oversodium sulfate. The sodium sulfate was filtered off and the solvent wasdistilled away. n-Hexane was added for crystallization. The crystalswere filtered off and then recrystallized from n-hexane. Thus there wasobtained 39.5 g of the exemplified compound (A-7) in the form ofcolorless crystals.

Yield: 75%, m.p. 121°-124° C.

IR (KBr, cm⁻¹): 3400, 1720, 1505, 1185, 872.

NMR (CDCl₃, δ): 6.85 (1H, s), 6.70 (1H, s), 6.55 (1H, s), 6.34 (1H, s),5.10 (1H, s), 4.90 (1H, s), 4.8-4.5 (1H, m), 4.17 (2H, t, J=6 Hz),3.15-2.85 (1H, m), 2.05 (3H, s), 2.0 (3H, s), 2.0-0.7 (30H, m).

M/S (m/e): 527 (M⁺)

Elemental analysis (C₃₂ H₄₇ O₆). Found: C: 72.77%; H: 8.82%; Calcd: C:72.48%; H: 8.79%.

EXAMPLE 4 Synthesis of compound 5

To 50 g (0.152 mol) of compound 1 was added 200 ml of toluene and 25 g(0.288 mol) of manganese dioxide, followed by heating under reflux for 2hours. The reaction solution was cooled with ice for crystallization,and the crystals were filtered off. Upon recrystallization from 300 mlof ethyl acetate, there was obtained 45.2 g of compound 5 in the form ofdark red crystals.

Yield: 91%, m.p. 215°-218° C.

Synthesis of compound 6

To 50 g (0.153 mol) of compound 5 was added 200 ml of dimethyl acetamidefor dissolution. To the resulting solution were added 12.5 ml (0.162mol) of methanesulfonyl chloride and then 22.5 ml (0.161 mol) oftriethylamine dropwise with stirring at 5°-10° C. over 30 minutes. Thereaction solution was poured into iced-water, followed by extractionwith 200 ml of ethyl acetate. The organic layer was washed with waterand dried over sodium sulfate. The sodium sulfate was filtered off andthe ethyl acetate was distilled away. Upon crystallization frommkethanol, there was obtained 45 g of compound 6 in the form ofcolorless crystals.

Yield: 72.6%, m.p. 133°-136° C.

Synthesis of compound 7

To 40.4 g (0.100 mol) of compound 6 was added 400 ml of ethyl acetatefor dissolution. To the resulting solution were added 18 g (0.202 mol)of diethylhydroxyamine with stirring at 20°-25° C., followed by stirringfor 2 hours. The reaction solution was poured into acid water (withhydrochloric acid), followed by extraction with ethyl acetate. Theorganic layer was washed with water and dried over sodium sulfate. Thesodium sulfate was filtered off and the ethyl acetate was distilledaway. Thus there was obtained 40.4 g of compound 7 in the form of crudeoil.

Yield: 99.5%.

Synthesis of compound 9

To 20.3 g (0.050 mol) of compound 7 was added 20 ml of acetonitrile and7.1 ml (0.075 mol) of acetic anhydride, followed by heating under refluxfor 8 hours. The reaction solution was evaporated to dryness underreduced pressure. To the resulting residues was added 100 ml of dimethylacetamide for dissolution. To the resulting solution were added 4.3 ml(0.055 mol) of methanesulfonyl chloride with stirring at 20°-25° C., and8.4 ml (0.060 mol) of triethylamine dropwise over 15 minutes. Stirringwas continued at 25°-30° C. for 30 minutes. The reaction solution waspoured into ice-cooled acid water (with hydrochloric acid), followed byextraction with 100 ml of ethyl acetate. The organic layer was washedwith water and dried over sodium sulfate. The sodium sulfate wasfiltered off and the ethyl acetate was distilled away. Uponcrystallization from methanol, there was obtained 24.7 g of compound 9in the form of colorless crystals.

Yield: 94%, m.p. 158° C.

Synthesis of compound 10

26.3% of compound 9 was added to a solution of 4.2 g of potassiumhydroxide in 84 ml of methanol, with stirring at 5°-10° C. Stirring wascontinued at 20°-25° C. for 1 hour. The reaction solution was pouredinto ice-cooled acid water (with hydrochloric acid), followed byextraction with 100 ml of ethyl acetate. The organic layer was washedwith water and dried over sodium sulfate. The sodium sulfate wasfiltered off and the ethyl acetate was distilled away. Thus there wasobtained 23.2 g of compound 10 in the form of viscosity oil.

Yield: 96%.

Synthesis of exemplified compound (A-10)

To 24.2 g (0.050 mol) of compound 10 was added 120 ml of dimethylacetamide for dissolution. While this solution was kept at 5° to 10° C.,2.4 g (0.060 mol) of sodium hydride (60% dispersion in oil) was addedwith stirring. Then 11.6 g (0.060 mol) of octyl bromide was addeddropwise, followed by stirring at 27° to 30° C. for 5 hours. Afteraddition of 20 ml of methanol, the reaction solution was poured intoice-cooled acid water (with hydrochloric acid), followed by extractionwith 150 ml of ethyl acetate. After thorough water washing, the ethylacetate was distilled away. To the resulting residues was added asolution of 11.2 g (0.200 mol) of potassium hydroxide in 112 ml ofmethanol, followed by heating under reflux for 4 hours. The reactionsolution was poured into ice-cooled acid water (with hydrochloric acid),followed by extraction with 150 ml of ethyl acetate. After waterwashing, the organic layer was dried over sodium sulfate. The sodiumsulfate was filtered off and the ethyl acetate was distilled away.n-Hexane was added for crystallization. The crystals were filtered offand then recrystallized from n-hexane. Thus there was obtained 15 g ofthe exemplified compound (A-10) in the form of colorless crystals.

Yield: 68%, m.p. 85°-87° C.

IR (KBr, cm⁻¹): 3380, 1505, 1180, 870.

NMR (CDCl₈, δ): 7.72 (1H, s), 6.68-6.60 (4H, m), 4.82 (1H, s), 3.82 (2H,t, J=6.7 Hz), 2.53 (1H, d, J=16 Hz), 2.15 (3H, s) 2.12 (3H, s), 1.98(1H, d, J=16 Hz), 1.65 (3H, s), 1.9-1.0 (12H, m), 1.10 (3H, s), 1.1-0.7(3H, m).

M/S (m/e): 441 (M⁺)

Elemental analysis (C₂₈ H₃₄ O₄).

Found: C: 76.23%; H: 9.28%; Calcd: C: 76.15%; H: 9.36%.

EXAMPLE 5

10 g of cyan coupler,2-{α-(1,4-di-tert-amylphenoxy)butylamido}-4,6-dichloro-5-methylphenolwas dissolved in 10 ml of tricresyl phosphate and 20 ml of ethylacetate. The resulting solution was emulsified and dispersed into 80 gof gelatin solution containing 8 ml of 1% aqueous solution of sodiumdodecylbenzenesulfonate.

The thus obtained emulsified dispersion was mixed with 145 g (7 g as Ag)or red sensitive silver chlorobromide (Br 50 mol%) emulsion. Sodiumdodecylbenzenesulfonate as a coating auxiliary was added. The resultingemulsion was coated on a paper support with both sides laminated withpolyethylene. The coating amount of the coupler was 400 mg/m².

The emulsion layer was further coated with a gelatin protective layer(gelatin 1 g/m²). Thus there was obtained Sample A.

Sample B to E were prepared in the same manner as mentioned above,except that an antioxidant (a compound of this invention or acomparative compound) was added in an amount of 50 mol% based on thecoupler as shown in Table 1.

Sample F was prepared in the same manner as mentioned above, except thatthe coupler was replaced by4-chloro-2-}2-(methanesulfonamide)-benzamide}-5-α-(3-pentadecylphenoxy)butylamidephenol.Samples G to J were prepared in the same manner as mentioned above,except that an antioxidant (a compound of this invention or acomparative compound) was added in an amount of 50 mol% based on thecoupler as shown in Table 1.

Each sample was exposed for 1 second at 1000 lux and treated with thefollowing processing solution.

    ______________________________________                                        Developing solution                                                           Benzyl alcohol           15       ml                                          Diethylenetriamine pentaacetic acid                                                                    5        g                                           KBr                      0.4      g                                           Na.sub.2 SO.sub.3        5        g                                           Na.sub.2 CO.sub.3        30       g                                           Hydroxylamine sulfate    2        g                                           4-amino-3-methyl-N--ethyl-N--β-(methane-                                                          4.5      g                                           sulfonamide)ethylaniline.3/2H.sub.2 SO.sub.4.H.sub.2 O                        Water to make 1000 ml    pH 10.1                                              Bleach-fixing solution                                                        Ammonium thiosulfate (70 wt %)                                                                         150      ml                                          Na.sub.2 SO.sub.3        5        g                                           Na [Fe(EDTA)]            40       g                                           EDTA                     4        g                                           Water to make 1000 ml    pH 6.8                                               ______________________________________                                        Processing step                                                                             Temperature    Time                                             ______________________________________                                        Development   33° C.  3 min 30 sec                                     Bleach-fix bath                                                                             33° C.  1 min 30 sec                                     Washing with water                                                                          28-35° C.                                                                             3 min                                            ______________________________________                                    

The dye image formed on each sample was examined for light fastness byexposing the sample to a xenon tester (100,000 lux) with anultraviolet-light absorbing filter (a production of Fuji Photo Film Co.,Ltd.) (400 nm and below) for 500 hours. The light fastness is expressedin terms of the residual dye density (percent) at an initial density of2.0 after exposure.

The dye image was also examined for heat fastness by keeping the sampleat 100° C. for 100 hours at a dark place. The heat fastness is expressedin terms of the residual dye density (percent) at an initial density of2.0.

The results are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                 Residual                                                                           After exposure                                                                        Residual                                                         dye  to xenon tester                                                                       dye  100° C.                                 Sample                                                                            Antioxidant                                                                            density                                                                            for 100 hours                                                                         density                                                                            100 hours                                                                          Remarks                                   __________________________________________________________________________    A   --       57%          51%       Control                                   B   Exemplified                                                                            86%          76%       This                                          Compound (A-5)                  inven-                                                                        tion                                      C   Exemplified                                                                            85%          78%       This                                          Compound (A-10)                 inven-                                                                        tion                                      D   2,6-di-tert-                                                                           60%          56%       Compar-                                       butyl-4-methyl                  ison                                          phenol                                                                    E   2,2,6,6-tetra-                                                                         58%          55%       Compar-                                       methyl-4-piperi-                ison                                          dinol                                                                     F   --       48%          94%       Control                                   G   Exemplified                                                                            85%          98%       This                                          Compound (A-3)                  inven-                                                                        tion                                      H   Exemplified                                                                            83%          97%       This                                          Compound (A-11)                 inven-                                                                        tion                                      I   2,6-di-tert-                                                                           53%          94%       Compar-                                       butyl-4-methyl                  ison                                          phenol                                                                    J   2,2,6,6-tetra-                                                                         59%          95%       Compar-                                       methyl-4-piperi-                ison                                          dinol                                                                     __________________________________________________________________________

EXAMPLE 6

Sample K was prepared in the same manner as in Example 5, except thatthe as the cyan couplerα-pyraloyl-2,4-dioxo-5,5-dimethyl-3-oxazolidinyl)-2-chloro-5-{.alpha.-(2,4-di-tert-aminophenoxy)-butylamido}acetanilidewas used and that a blue-sensitive silver chlorobromide (Br 80 mol%)emulsion was used in place of red-sensitive silver chlorobromideemulsion. Samples L to O were prepared in the same manner as mentionedabove, except that an antioxidant (a compound of this invention or acomparative compound) was added in an amount of 50 mol% based on thecoupler as shown in Table 2.

The samples were exposed and developed in the same manner as in Example5.

The dye image formed on each sample was examined for light fastness byexposing the sample to a xenon tester for 200 hours. The light fastnessis expressed in terms of the residuan dye density (percent) at aninitial density of 2.0 after exposure.

The dye image was also examined for heat fastness by keeping the sampleat 100° C. for 500 hours at a dark place. The heat fastness is expressedin terms of residual dye density (percent) at an initial density of 2.0.

The results are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                 Residual                                                                           After exposure                                                                        Residual                                                         dye  to xenon tester                                                                       dye  100° C.                                 Sample                                                                            Antioxidant                                                                            density                                                                            for 200 hours                                                                         density                                                                            500 hours                                                                          Remarks                                   __________________________________________________________________________    K   --       74%          91%       Control                                   L   Exemplified                                                                            93%          98%       This                                          Compound (A-5)                  inven-                                                                        tion                                      M   Exemplified                                                                            91%          97%       This                                          Compound (A-10)                 inven-                                                                        tion                                      N   2,6-di-tert-                                                                           76%          91%       Compar-                                       butyl-4-methyl-                 ison                                          phenol                                                                    O   2,2,6,6-tetra-                                                                         74%          92%       Compar-                                       methyl-4-piperi-                ison                                          dinol                                                                     __________________________________________________________________________

It is noted from Table 1 and 2 that the compound of this inventionexhibits an outstanding antioxidizing effect.

EXAMPLE 7

IIR (Polysar Butyl #100, degree of unsaturation 0.7%, a product ofPolymer Corp.) was compounded according to the following formulation.

    ______________________________________                                                         parts by weight                                              ______________________________________                                        Polysar Butyl #100 100                                                        Hard clay          120                                                        Zinc oxide         5                                                          Stearic acid       2                                                          Sulfur             1                                                          Tetramethylthiuram disulfide                                                                     2                                                          SRF carbon         10                                                         Mercaptobenzothiazole                                                                            0.5                                                        ______________________________________                                    

The compounded rubber was roll-milled and press-cured at 160° C. for 45minutes to make a 2 mm thick sheet. Test specimen (a) conforming to JISNo. 3 dumbell was punched out of this sheet.

In the same manner as above, there were prepared test specimens (b) to(e) each containing 1.5 parts by weight of antioxidant as shown in Table3.

The specimens were subjected to accelerated aging at 120° C. for 100hours in a Geer oven. The aging resistance was evaluated by the ratio ofthe tensile strength (kg/mm²) and elongation (%) measured after aging tothose measured before aging, and was expressed in terms of risidualvalue (%). The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                     Aging properties                                                                    Residual   Residual                                                           Cencile    elongation                                      Sample                                                                              Antioxidant  strength (%)                                                                             (%)     Remarks                                 ______________________________________                                        a     --           58         25      Control                                 b     Comparative  71         53      Compari-                                      compound                        son                                     c     Exemplified  97         96      This                                          compound (A-5)                  invention                               d     Exemplified  95         94      This                                          compound (A-7)                  invention                               e     Exemplified  96         95      This                                          compound (A-10)                 invention                               ______________________________________                                         ##STR28##     (The compound described in Japanese Patent Application (OPI) No.     14771/1977.)

It is noted from Table 3 that the compound of this invention is by farsuperior to the other compounds of similar structure when used as anantioxidant.

EXAMPLE 8

10 g of comparative magenta coupler (a),1-(2,4,6-trichlorophenyl)-3-{(2-chloro-5-tetradecanamido)anilino}-2-pyrazolin-5-onwas dissolved in 20 ml of tricresyl phosphate and 20 ml of ethylacetate. The resulting solution was emulsified and dispersed into 80 gof gelatin solution containing 8 ml of 1% aqueous solution of sodiumdodecylbenzenesulfonate.

The thus obtained emulsified dispersion was mixed with 145 g (7 g as Ag)of green-sensitive silver chlorobromide (Br 50 mol%) emulsion. Sodiumdodecylbenzenesulfonate as a coating auxiliary was added. The resultingemulsion was coated on a paper support with both sides laminated withpolyethylene. The coating amount of the coupler was 400 mg/m².

The emulsion layer was further coated with a gelatin protective layer(gelatin 1 g/m²). Thus there was obtained Sample A.

Samples B to W were prepared in the same manner as mentioned above,except that each of them was incorporated with a magenta coupler of thisinvention or a comparative magenta coupler and a compound of formula (I)of this invention or a comparative compound as shown in Table 4. Theamount of the compound of formula (I) or comparative compound was 50mol% based on the amount of the magenta coupler.

Each sample was exposed for 1 second at 1000 lux and treated with thefollowing processing solutions.

    ______________________________________                                        Developing solution                                                           Benzyl alcohol           15       ml                                          Diethylenetriamine pentaacetic acid                                                                    5        g                                           KBr                      0.4      g                                           Na.sub.2 SO.sub.3        5        g                                           Na.sub.2 CO.sub.3        30       g                                           Hydroxylamine sulfate    2        g                                           4-amino-3-methyl-N--ethyl-N--β-(methane-                                                          4.5      g                                           sulfonamide)ethylaniline.3/2H.sub.2 SO.sub.4.H.sub.2 O                        Water to make 1000 ml    pH 10.1                                              Bleach-fixing solution                                                        Ammonium thiosulfate (70 wt %)                                                                         150      ml                                          Na.sub.2 SO.sub.3        5        g                                           Na [Fe(EDTA)]            40       g                                           EDTA                     4        g                                           Water to make 1000 ml    pH 6.8                                               ______________________________________                                        Processing step                                                                           Temperature   Time                                                ______________________________________                                        Developing  33° C. 3 minute 30 second                                  Bleach-fixing                                                                             33° C. 1 minute 30 second                                  Washing     28-35° C.                                                                            3 minute                                            ______________________________________                                    

The dye image formed on each sample was examined for light fastness byexposing the sample to a xenon tester (200,000 lux) with an ultra-violetlight absorbing filter (a product of Fuji Photo Film Co., Ltd.)(absorbing the light of 400 nm and below) for 6 days.

The results are shown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________                             Change in                                                                     magenta                                                                       density                                                                              Change in density                                 Magenta     Discoloration                                                                          (Initial                                                                             of yellowing in                               Sample                                                                            coupler     inhibitor                                                                              density: 2.0)                                                                        white background                                                                       Remarks                              __________________________________________________________________________    A   Comparative coupler (a)                                                                   --       -1.75  +0.31    Comparative                                                                   example                              B   "           Exemplified                                                                            -0.48  +0.11    Comparative                                          compound (A-1)           example                              C   "           Exemplified                                                                            -0.45  +0.13    Comparative                                          compound (A-20)          example                              D   Comparative coupler (b)                                                                   --       -1.70  +0.34    Comparative                                                                   example                              E   "           Exemplified                                                                            -0.47  +0.10    Comparative                                          compound (A-4)           example                              F   "           Exemplified                                                                            -0.46  +0.13    Comparative                                          compound (A-5)           example                              G   Comparative coupler (c)                                                                   --       -1.80  +0.38    Comparative                                                                   example                              H   "           Exemplified                                                                            -0.67  +0.20    Comparative                                          compound (A-5)           example                              I   "           Exemplified                                                                            -0.69  +0.25    Comparative                                          compound (A-10)          example                              J   Comparative coupler (d)                                                                   --       -1.82  +0.44    Comparative                                                                   example                              K   "           Exemplified                                                                            -0.66  +0.23    Comparative                                          compound (A-7)           example                              L   "           Exemplified                                                                            -0.64  +0.26    Comparative                                          compound (A-11)          example                              M   M-16        --       -1.77  +0.32    Comparative                                                                   example                              N   "           Exemplified                                                                            -0.20  +0.06    This                                                 compouund (A-5)          invention                            O   "           Exemplified                                                                            -0.19  +0.08    This                                                 compound (A-10)          invention                            P   "           Comparative                                                                            -0.78  +0.31    Comparative                                          compound (1)             example                              Q   M-17        --       -1.78  +0.33    Comparative                                                                   example                              R   "           Exemplified                                                                            -0.21  +0.07    This                                                 compound (A-3)           invention                            S   "           Exemplified                                                                            -0.19  +0.05    This                                                 compound (A-5)           invention                            T   "           Comparative                                                                            -0.71  +0.30    Comparative                                          compound (2)             example                              U   "           Comparative                                                                            -0.61  +0.09    Comparative                                          compound (3)             example                              V   "           Comparative                                                                            -1.02  +0.31    Comparative                                          compound (4)             example                              W   "           Comparative                                                                            -0.83  +0.32    Comparative                                          compound (5)             example                              __________________________________________________________________________     ##STR29##

Coupler disclosed in U.S. Pat. No. 4,264,780 ##STR30##

Coupler disclosed in U.S. Pat. No. 4,264,720 ##STR31##

Coupler disclosed in U.S. Pat. No. 4,264,720 ##STR32##

Coupler disclosed in Japanese Patent Application (OPI) No. 204037/1982##STR33##

Compound disclosed in U.S. Pat. No. 3,432,300 ##STR34##

Compound disclosed in U.S. Pat. No. 3,698,909 ##STR35##

Compound disclosed in U.S. Pat. No. 4,113,495 ##STR36##

Compound disclosed in U.S. Pat. No. 3,930,866 and West Germany Patent(OLS) No. 2,146,668 ##STR37##

Compound disclosed in U.S. Pat. No. 4,254,216

As is apparent from the results of Table 4, the compound of formula (I)shows the superior effect of improving light fastness to the knownsimilar compounds. The effect is remarkable when it is combined with a5-pyrazolone type magenta coupler having the splitting-off group offormula (II).

EXAMPLE 9

Sample (a) of color photographic material was prepared by coating sevenlayers one over another on a paper support with both sides laminatedwith polyethylene, as shown in Table 5. (The coating weight is indicatedin terms of g/m².)

                  TABLE 5                                                         ______________________________________                                        7th layer                                                                              Gelatin              1,000  mg/m.sup.2                               (Protective                                                                   layer)                                                                        6th layer                                                                              UV light absorbent (*1)                                                                            600    mg/m.sup.2                               (UV light                                                                              Solvent for UV light absorbent (*2)                                                                300    mg/m.sup.2                               absorber)                                                                              Gelatin              800    mg/m.sup.2                               5th layer                                                                              Silver chloro-bromide emulsion                                                                     300    mg/m.sup.2                               (Red-sensitive                                                                         (silver bromide 50 mol %)                                            layer)   Cyan coupler (*3)    400    mg/m.sup.2                                        Coupler solvent (*2) 400    mg/m.sup.2                                        Gelatin              1,000  mg/m.sup.2                               4th layer                                                                              UV light absorbent (*1)                                                                            600    mg/m.sup.2                               (Intermediate                                                                          Solvent for UV light absorbent (*2)                                                                300    mg/m.sup.2                               layer)   Gelatin              800    mg/m.sup.2                               3rd layer                                                                              Silver chlorobromide emulsion (silver                                                              200    mg/m.sup.2                               (Green-  bromide 70 mol %) silver                                             sensitive                                                                              Magenta coupler (*4) 300    mg/m.sup.2                               layer)   Coupler solvent (*5) 200    mg/m.sup.2                                        Gelatin              1,000  mg/m.sup.2                               2nd layer                                                                              Gelatin              1,000  mg/m.sup.2                               (Intermediate                                                                 layer)                                                                        1st layer                                                                              Silver chlorobromide emulsion (silver                                                              400    mg/m.sup.2                               (Blue-   bromide 80 mol %) silver                                             sensitive                                                                              Yellow coupler (*6)  300    mg/m.sup.2                               layer)   Coupler solvent (*7) 150    mg/m.sup.2                                        Gelatin              1,200  mg/m.sup.2                               Support  Paper support polyethylene-laminated (both sides)                    ______________________________________                                         Note to Table 5                                                               (*1) UV light absorbent:                                                      2(2-hydroxy-2-sec-butyl-5-tert-butylphenyl)-benzotriazole                     (*2) Solvent: dibutyl phthalate                                               (*3) Coupler:                                                                 2[(2,4-di-tert-pentylphenoxy)butanamido]4,6dichloro-5-methylphenol            (*4) Coupler: 1(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecano              amido)anilino4-(2-butoxy-5-tert-octylphenylthio)-2-pyrazolin-5-on             (*5) Solvent: tricresyl phosphate                                             (*6) Coupler:                                                                 pyvaloyl-(2,4-dioxy-5,5dimethyloxazolidin-3-yl)-2-chloro-5-[(2,4-di-tert-    entyloxy)butanamido] acetanilide                                               (*7) Solvent: dioctylbutyl phosphate                                     

Sample (b) to (k) were prepared in the same manner as above except thatthe third layer was incorporated with one or two kinds of discolorationinhibitors as shown in Table 6.

Each sample was exposed to green light through a continuous wedge andprocessed in the same manner as in Example 8. The dyes thus formed wereexamined for light fastness by exposure to a fluorescent fading tester(20,000 lux) for 4 weeks. The results are shown in Table 6.

                                      TABLE 6                                     __________________________________________________________________________                       Amount added                                                                           Change in magenta                                                    (mol % based on                                                                        density (initial                                  Sample                                                                            Discoloration inhibitor                                                                      coupler) density: 1.0)                                                                           Remarks                                 __________________________________________________________________________    a   --             --       -0.78     Comparative                                                                   example                                 b   Exemplified compound (A-5)                                                                   50       -0.11     This                                                                          invention                               c   Exemplified compound                                                                         50       -0.12     This                                        (A-10)                            invention                               d   Exemplified compound (G-3)                                                                   50       -0.23     Comparative                                                                   example                                 e   Exemplified compound                                                                         50       -0.31     Comparative                                 (G-12)                            example                                 f   Exemplified compound                                                                         50       -0.39     Comparative                                 (G-15)                            example                                 g   Exemplified compound                                                                         50       -0.68     Comparative                                 (G-16)                            example                                 h   Exemplified compound (A-5)                                                                   50       -0.06     This                                        Exemplified compound (G-3)                                                                   50                 invention                               i   Exemplified compound (A-5)                                                                   50       -0.05     This                                        Exemplified compound (G-12)                                                                  50                 invention                               j   Exemplified compound (A-5)                                                                   50       -0.05     This                                        Exemplified compound (G-15)                                                                  50                 invention                               k   Exemplified compound (A-5)                                                                   50       -0.07     This                                        Exemplified compound (G-16)                                                                  50                 invention                               __________________________________________________________________________

It is noted from Table 6 that the compound of formula (I) shows superioreffect of improving light fastness to the known discoloration inhibitor,in combination with a 5-pyrazolone type magenta coupler having the grouprepresented by formula (II). This effect is further remarkable when itis used in combination with a known discoloration inhibitor.

EXAMPLE 10

Sample (l), (m), and (n) were prepared in the same manner as in Sample(b) of Example 9, except that the third layer is incorporated with amagenta coupler (M-17) and a discoloration inhibitor (A-5) of thisinvention, as shown in Table 7. They were exposed and developed,together with Samples (a) and (b), in the same manner as in Example 9.

                  TABLE 7                                                         ______________________________________                                        Sample  Points changed                                                        ______________________________________                                        g       Same as the sample shown in Table 5 of Example 9                              except that as the cyan coupler is replaced by                                2-[α-(2,4-di-tert-pentylphenoxy)-butanamido-4,6-                        dichloro-5-ethylphenol.                                               h       Same as the sample shown in Table 5 of Example 9                              except that the cyan coupler is replaced by an                                equimolar mixture of the coupler in sample (g) and                            5-[2-(4-tert-amyl-2-chlorophenoxy)octanamido]-4-                              chloro-2-(2-chlorobenzamido)phenol. The coating                               weight is 1.1 times more than that in Table 5.                        i       Same as the sample shown in Table 5 of Example 9                              except that the yellow coupler is incorporated                                with 20 mol % (based on the yellow coupler) of                                bis-[2,2,6,6-tetramethyl-1-(1-oxo-2-propenyl)-4-                              piperidinyl]-1,1-bis-[(3,5-di-tert-butyl-4-                                   hydroxyphenyl)methyl]-propanediol.                                    ______________________________________                                    

The dye image thus obtained was stored at 100° C. for 7 days to findthat the magenta density remained almost unchanged. After storage at 60°C. and 90%RH for 6 weeks the magenta density changed very little. Therewas very little stain in the white background. These results are shownin Table 8.

                  TABLE 8                                                         ______________________________________                                        Change in magenta density (initial density = 1.0)                             Sample at 100° C. for 7 days                                                                at 60° C., 90% RH for 6 weeks                     ______________________________________                                        a      0.95 (0.16)   0.96 (0.17)                                              b      0.99 (0.14)   0.98 (0.15)                                              l      0.99 (0.14)   0.98 (0.15)                                              m      0.98 (0.13)   0.99 (0.14)                                              n      1.00 (0.14)   0.98 (0.14)                                              ______________________________________                                         Note:                                                                         Each value in parenthesis indicates the density (stain) of the white          background measured through a blue filter.                               

It is noted from Table 8 that the 5-pyrazolone type magenta couplerhaving the splitting-off group of formula (II) forms a color image whichis stable to heat and/or humidity and also forms a white backgroundwhich is stable with respect to stain. This effect remains unchangedeven when the composition in the adjacent layer is changed.

EXAMPLE 11

10 g of magenta coupler,1-(2,4,6-trichlorophenyl)-3-{(2-chloro-5-tetradecanamido)anilino}-2-pyrazolin-5-onwas dissolved in 20 ml of tricresyl phosphate and 20 ml of ethylacetate. The resulting solution was emulsified and dispersed into 80 gof gelatin solution containing 8 ml of 1% aqueous solution of sodiumdodecylbenzenesulfonate.

The thus obtained emulsified dispersion was mixed with 145 g (7 g as Ag)of green-sensitive silver chlorobromide (Br 50 mol%) emulsion. Sodiumdodecylbenzenesulfonate as a coating auxiliary was added. The resultingemulsion was coated on a paper support with both sides laminated withpolyethylene. The coating amount of the coupler was 400 mg/m².

The emulsion layer was further coated with a gelatin protective layer(gelatin 1 g/m²). Thus there was obtained Sample A.

Samples B to Q were prepared in the same manner as mentioned above,except that each of them was incorporated with a mixture of the couplerof formula (IX) of this invention and the compound of formula (I) or acomparative compound as shown in Table 9. The amount of the compound offormula (I) or comparative compound was 50 mol% based on the amount ofthe coupler used.

Each sample was exposed for 1 second at 1000 lux and treated with thefollowing processing solutions.

    ______________________________________                                        Developing solution                                                           Benzyl alcohol           15       ml                                          Diethylenetriamine pentaacetic acid                                                                    5        g                                           KBr                      0.4      g                                           Na.sub.2 SO.sub.3        5        g                                           Na.sub.2 CO.sub.3        30       g                                           Hydroxylamine sulfate    2        g                                           4-amino-3-methyl-N--ethyl-N--β-(methane-                                                          4.5      g                                           sulfonamide)ethylaniline.3/2H.sub.2 SO.sub.4.H.sub.2 O                        Water to make 1000 ml    pH 10.1                                              Bleach-fixing solution                                                        Ammonium thiosulfate (70 wt %)                                                                         150      ml                                          Na.sub.2 SO.sub.3        5        g                                           Na [Fe(EDTA)]            40       g                                           EDTA                     4        g                                           Water to make 1000 ml    pH 6.8                                               ______________________________________                                        Processing step                                                                             Temperature  Time                                               ______________________________________                                        Developing    33° C.                                                                              3 minute 30 second                                 Bleach-fixing 33° C.                                                                              1 minute 30 second                                 Washing with water                                                                          28-35° C.                                                                           3 minute                                           ______________________________________                                    

The dye image formed on each sample was examined for light fastness byexposing the sample to a xenon tester (200,000 lux) with an ultra-violetlight absorbing filter (a product of Fuji Photo Film Co., Ltd.)(absorbing 400 nm and below) for 5 days. Change in density (initialdensity: 2.0) was measured with a Macbeth densitometer RD-514 (withstatus AA filter). The results are shown in Table 9.

                                      TABLE 9                                     __________________________________________________________________________                      Change in                                                                     magenta                                                                       density                                                                              Change in density                                        Magenta                                                                            Discoloration                                                                          (Initial                                                                             in white background                                  Sample                                                                            coupler                                                                            inhibitor                                                                              density: 2.0)                                                                        by yellowing                                                                            Remarks                                    __________________________________________________________________________    A   M-25 --       -1.54  +0.27     Comparative                                                                   example                                    B   "    Comparative                                                                            -0.42  +0.10     Comparative                                         compound (1)              example                                    C   "    Comparative                                                                            -0.51  +0.11     Comparative                                         compound (2)              example                                    D   "    Comparative                                                                            -0.49  +0.11     Comparative                                         compound (3)              example                                    E   "    Comparative                                                                            -0.57  +0.07     Comparative                                         compound (4)              example                                    F   "    Comparative                                                                            -0.71  +0.26     Comparative                                         compound (5)              example                                    G   "    Exemplified                                                                            -0.27  +0.06     This                                                compound (A-3)            invention                                  H   "    Exemplified                                                                            -0.25  +0.05     This                                                compound (A-5)            invention                                  I   "    Exemplified                                                                            -0.26  +0.06     This                                                compound (A-10)           invention                                  J   "    Exemplified                                                                            -0.22  +0.04     This                                                compound (A-17)           invention                                  K   M-31 --       -1.46  +0.25     Comparative                                                                   example                                    L   "    Comparative                                                                            -0.70  +0.23     Comparative                                         compound (6)              example                                    M   "    Comparative                                                                            -0.72  +0.27     Comparative                                         compound (7)              example                                    N   "    Exemplified                                                                            -0.27  +0.07     This                                                compound (A-3)            invention                                  O   "    Exemplified                                                                            -0.26  +0.05     This                                                compound (A-4)            invention                                  P   "    Exemplified                                                                            -0.24  +0.05     This                                                compound (A-7)            invention                                  Q   "    Exemplified                                                                            -0.25  +0.06     This                                                compound (A-12)           invention                                  __________________________________________________________________________     ##STR38##

Compound disclosed in U.S. Pat. No. 4,264,720 ##STR39##

Compound disclosed in U.S. Pat. No. 4,264,720 ##STR40##

Compound disclosed in U.S. Pat. No 4,264,720 ##STR41##

Compound disclosed in U.S. Pat. No. 4,113,495 ##STR42##

Compound disclosed in U.S. Pat. No. 3,432,300 ##STR43##

Compound disclosed in U.S. Pat. No. 3,698,909 ##STR44##

Compound disclosed in U.S. Pat. No. 3,930,866 and West Germany PatentApplication (OLS) No. 2,146,668

It is noted from Table 9 that the samples of this invention are superiorin the prevention of fading by light to the comparative samplesincorporated with a known discoloration inhibitor of the similarstructure. In addition, they are superior in the prevention of yellowingby light in the white background portion.

EXAMPLE 12

Sample (a) of color photographic material was prepared by coating sevenlayers one over another on a paper support with both sides laminatedwith polyethylene, in the same manner as described in Table 5 of Example9 except that in the 3rd layer magenta coupler M-25 is added to.

Samples (b) to (f) were prepared in the same manner as above except thatthe third layer was incorporated with one or two kinds of discolorationinhibitors as shown in Table 10.

Each sample was exposed to green light through a continuous wedge andprocessed in the same manner as in Example 8. The dye images thus formedwere examined for light fastness by exposure to a fluorescent fadingtester (20,000 lux) for 4 weeks. The results are shown in Table 10.

                                      TABLE 10                                    __________________________________________________________________________                      Amount added                                                                          Change in magenta                                                     (mol % based                                                                          density (initial                                    Sample                                                                            Discoloration inhibitor                                                                     on coupler)                                                                           density: 1.0)                                                                           Remarks                                   __________________________________________________________________________    a   --            --      -0.51     Comparative                                                                   example                                   b   Exemplified compound (A-5)                                                                  50      -0.08     This                                                                          invention                                 c     "           100     -0.05     This                                                                          invention                                 d   Comparative compound (1)                                                                    50      -0.18     Comparative                                                                   example                                   e     "           100     -0.17     Comparative                                                                   example                                   f   Exemplified compound (A-5)                                                                  50      -0.04     This                                          2,5-di-tert-octylhydrquinone                                                                50                invention                                 __________________________________________________________________________

It is noted from Table 11 that the sample of this invention is superiorin the prevention of discoloration by light. The effect is enhanced whenthe amount of the discoloration inhibitor is increased.

EXAMPLE 13

Samples (g), (h), and (i) were prepared in the same manner as in Sample(b) of Example 12, in which third layer is incorporated with a magentacoupler (M-25) and a discoloration inhibitor (A-5), except that thefifth or first layer was changed as shown in Table 11. They were exposedand developed, together with Samples (a) and (b), in the same manner asin Example 12.

                  TABLE 11                                                        ______________________________________                                        Sample  Points changed                                                        ______________________________________                                        g       Same as the sample shown in Example 12, except                                that the cyan coupler in the fifth layer is                                   replaced by 2-[α-(2,4-di-tert-pentylphenoxy)-                           butanamido-4,6-dichloro-5-ethylphenol.                                        (Refer to Table 5 of Example 9).                                      h       Same as the sample shown in Example 12, except                                that the cyan coupler in the fifth layer is                                   replaced by an equimolar mixture of the coupler                               in sample (g) and 5-[2-(4-tert-amyl-2-                                        chlorophenoxy)-octanamido]-4-chloro-2-(2-                                     chlorobenzamide)phenol. The coating weight is                                 1.1 times more than that in Table 5 of Example 9.                     i       Same as the sample shown in Example 12, except                                that the yellow coupler in the first layer is                                 incorporated with 20 mol % (based on the yellow                               coupler) of bis[2,2,6,6-tetramethyl-1-(1-oxo-2-                               propenyl)-4-piperidinyl]-1,1-bis[(3,5-di-tert-                                butyl-4-hydroxyphenyl)-methyl]-propanediol.                                   (Refer to Table 5 of Example 9).                                      ______________________________________                                    

The dye image thus obtained was stored at 100° C. for 7 days to findthat the magenta density remained almost unchanged. After storage at 60°C. and 90%RH for 6 weeks the magenta density changed very little. Therewas very little stain in the white background portion (See Table 12).

                  TABLE 12                                                        ______________________________________                                        Change in magenta density (initial density = 1.0)                             Sample at 100° C. for 7 days                                                                at 60° C., 90% RH for 6 weeks                     ______________________________________                                        a      0.94 (0.38)   0.93 (0.43)                                              b      0.97 (0.17)   0.97 (0.17)                                              g      0.97 (0.14)   0.98 (0.16)                                              h      0.98 (0.15)   0.98 (0.15)                                              i      0.99 (0.14)   0.98 (0.16)                                              ______________________________________                                         Note:                                                                         Each value in parenthesis indicates the density (stain) of the white          background measured through a blue filter.                               

It is noted from Table 12 that the 3-anilino-5-pyrazolone type magentarepresented by formula (IX) forms a color image which is stable to heatand/or humidity and also forms a white background which is stable withrespect to stain. This effect remains unchanged even when thecomposition in the adjacent layer is changed.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that the invention is not limited to the specific embodimentsthereof except as defined in the appended claims.

What is claimed is:
 1. A silver halide color photographic materialcomprising at least one silver halide emulsion layer having associatedtherewith at least one compound represented by formula (X) and at leastone pyrazolone type magenta coupler having at the coupling positionthereof a coupling off group represented by formula (II) ##STR45##wherein R represents an alkyl group or an aryl group; each pair of R₃and R₃ has the same meaning and represents a hydrogen atom, alkyl group,aryl group, alkoxy group, aryloxy group, alkylthio group, arylthiogroup, acylamino group, diacylamino group, sulfonamido group, alkylaminogroup, acyl group, alkoxycarbonyl group, acyloxy group, or halogen atom;R₂₃ and R₂₄ each represents a hydrogen atom or alkyl group, providedthat both of them are not hydrogen atoms or alkyl groups at the sametime and when R and R₃ are alkyl groups or aryl groups or those groupscontaining partially alkyl groups or aryl groups, such alkyl groups oraryl groups may be further substituted by other substituent groups. 2.The silver halide color photographic material as described in claim 1,wherein the pyrazolone type magenta coupler is selected from thecompounds represented by formula (III) ##STR46## wherein R has the samemeaning as in formula (II); Ar₁ represents an aryl group; and Zrepresents an acylamino group, anilino group, or ureido group.
 3. Thesilver halide color photographic material as described in claim 2,wherein the pyrazolone type magenta color is selected from the compoundsrepresented by formula (IV) ##STR47## wherein R has the same meaning asin formula (II); Ar₂ represents a phenyl group having at least onesubstituent selected from the group consisting of a halogen atom, alkylgroup, alkoxy group, alkoxycarbonyl, or cyano group; R₆ represents ahalogen atom or alkoxy group; R₇ represents a hydrogen atom, halogenatom, alkyl group, alkoxy group, acylamino group, sulfonamido group,sulfamoyl group, carbamoyl group, diacylamino group, alkoxycarbonylgroup, alkoxysulfonyl group, aryloxysulfonyl group, alkanesulfonylgroup, arylsulfonyl group, alkylthio group, arylthio group,alkyloxycarbonylamino group, alkylureido group, acryl group, nitrogroup, carboxyl group, or trichloromethyl group; and l is an integer of1 to 4 with the proviso that when l is greater than 1, the groupsrepresented by R₇ may be the same or different.
 4. The silver halidecolor photographic material as described in claim 3, wherein thepyrazolone type magenta coupler is selected from the compoundsrepresented by formula (V), (VI) or (VII): ##STR48## wherein R₈ denotesa halogen atom, hydroxyl group, alkyl group, alkoxyl group, or arylgroup; R₉ denotes a hydrogen atom, halogen atom, hydroxyl group, alkylgroup, alkoxyl group, or aryl group with the proviso that at least oneof R₈ and R₉ is an alkoxyl group; R₁₀ denotes an alkyl group or arylgroup; R₁₁ denotes a halogen atom; alkyl group, alkoxyl group, or arylgroup; m is an integer of 1 to 4, and n is an integer of 1 to 5 with theproviso that when m or n is greater than 1, the groups represented by R₉or R₁₁ may be the same or different; R₁₂ denotes a hydrogen atom, alkylgroup or aryl group; R₁₃ denotes a hydrogen atom, alkyl group, arylgroup, alkoxyl group, aryloxy group, alkoxycarbonyl group,aryloxycarbonyl group, carbamoyl group, acyl group, or carboxyl group;X₁ denotes an alkylene group, alkenylene group, arylene group, ##STR49##R₁₄ denotes a hydrogen atom, alkyl group, aryl group, or heterocyclicgroup.
 5. The silver halide color photographic material as described inclaim 4, wherein the sum of the carbon atoms for R₁₃ and R₁₄ is as least12.
 6. The silver halide color photographic material as described inclaim 3, wherein the pyrazolone type magenta coupler is selected fromthe compounds represented by formula (VIII) below ##STR50## wherein Ar₂,R₆, and R₇ have the same meaning as in formula (IV); R₉ represents ahydrogen atom, halogen atom, hydroxyl group, alkyl group, alkoxy group,or aryl group; m is an integer of 1 to 4; R₁₅ represents an aliphaticgroup or aromatic group which may have (a) a halogen atom, (b) a cyanogroup, (c) an aliphatic, aromatic, or heterocyclic sulfonyl group,sulfinyl grup, or sulfonyl group, (d) ##STR51## or (e) --(A₂ --M)mB₂wherein A₁ denotes a single bond, oxygen atom, sulfur atom, imino group,or divalent aliphatic, aromatic, or heterocyclic group; B₁ denotes ahydroxyl group, aliphatic or aromatic oxy group, hydrogen atom,aliphatic group, aromatic group, heterocyclic group, or acyclic aminogroup or hydrazino group which may have a substituent group; A₂ denotesa single bond, or divalent aliphatic, aromatic, or heterocyclic group;B₂ denotes a hydrogen atom, aliphatic group, aromatic group orheterocyclic group; M denotes an oxygen atom, sulfur atom, or iminogroup; and m denotes an integer of 1 to
 4. 7. The silver halide colorphotographic material as described in claim 3, wherein:Ar₂ is asubstituted phenyl group wherein the substituent group is selected fromthe group consisting of a halogen atom, an alkyl group having 1 to 22carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, analkoxycarbonyl group having 2 to 23 carbon atoms and a cyano group. 8.The silver halide color photographic material as described in claim 1,wherein the compound represented by formula (X) is included in an amountof 100 to 200 mol% based on the pyrazolone type magenta coupler.
 9. Thesilver halide color photographic material as described in claim 1,wherein the pyrazolone type magenta coupler is added in an amount of2×10⁻³ to 5×10⁻¹ mol per 1 mol of silver.
 10. A silver halide colorphotographic material comprising at least one silver halide emulsionlayer having associated therewith at least one kind of the compoundselected from the compounds represented by the formula (X) and at leastone pyrazolone type magenta coupler represented formula (IX) ##STR52##wherein R₃ represents a methyl group; R₂₃ and R₂₄ each represents ahydrogen atom or alkyl group, provided that one of R₂₃ and R₂₄ is ahydrogen atom and that both of them are not hydrogen atoms at the sametime; Ar₃ represents an aryl group; R₂₅ represents a halogen atom oralkoxy group; and R₂₆ and R₂₇ each represents a hydrogen atom, halogenatom, alkyl group, alkoxy group, acylamino group, sulfonamide group,sulfamoyl group, carbamoyl group, diacylamino group, alkoxycarbonylgroup, alkoxysulfonyl group, aryloxysulfonyl group, alkanesulfonylgroup, arysulfonyl group, alkylthio group, arylthio group,alkyloxycarbonylamino group, alkylureido group, acyl group, nitro group,carboxyl group, or trichloromethyl group.
 11. The silver halide colorphotographic material as described in claim 10, wherein Ar₃ in formula(IX) is a phenyl group having at least one substituent selected from ahalogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, or cyanogroup.
 12. The silver halide color photographic material as described inclaim 10, wherein the compound represented by formula (X) is included inan amount of 100 to 200 mol% based on the 5-pyrazolone type magentacoupler.
 13. The silver halide color photographic material as describedin claim 10, wherein the 5-pyrazolone type magenta coupler is added inan amount of 2×10⁻³ to 5×10⁻¹ mol per 1 mol of silver.
 14. The silverhalide color photographic material as described in claim 1, furthercomprising at least one cyan coupler represented by formula (XII) or(XIII) ##STR53## wherein R₃₆, R₃₇, and R₃₉ represent substituted orunsubstituted aliphatic, aromatic, or heterocyclic groups; R₃₈ and R₄₁represent hydrogen atoms, halogen atoms, aliphatic groups, aromaticgroups, or acylamino groups; R₃₈ represents a group of nonmetallic atomswhich forms, together with R₃₇, a nitrogen-containing 5- or 6-memberedring; R₄₀ represents an aliphatic group having at least 2 carbon atomswhich may be further substituted; Y₃₁ and Y₃₂ represent hydrogen atomsor the groups that can be split-off upon an oxidation coupling reactionwith the developint agent; and n is 0 or
 1. 15. The silver halide colorphotographic material as described in claim 14, wherein:R₃₆ is an arylgroup further substituted by a halogen atom, an alkyl group, an alkoxylgroup, an aryloxy group, an acylamino group, an acyl group, a carbamoylgroup, a sulfonamido group, a sulfamoyl group, a sulfonyl group, asulfamido group, an oxycarbonyl group, or a cyano group; R₃₇ is asubstituted or unsubstituted alkyl group or aryl group; R₃₈ is ahydrogen atom; R₃₉ is a substituted or unsubstituted alkyl group or arylgroup; R₄₀ is an alkyl group having 2 to 15 carbon atoms or a methylgroup having a substituent having 1 or more carbon atoms; R₄₁ is ahydrogen atom or halogen atom; and Y₃₁ and Y₃₂ are a hydrogen atom, ahalogen atom, an alkoxyl group, an aryloxy group, an acyloxy group, or asulfonamido group.
 16. The silver halide color photographic material asdescribed in claim 1, further comprising at least one yellow couplerrepresented by formula (XIV) ##STR54## wherein R₄₂ denotes a substitutedor unsubstituted N-phenylcarbamoyl group; Z₁ denotes a hydrogen atom ora group which is split-off upon coupling reaction with an oxidationproduct of the developing agent; and a dimer or polymer may be formedthrough Z₁.
 17. The silver halide color photographic material asdescribed in claim 16, wherein R₄₂ is represented by formula (XV)##STR55## wherein G₁ represents a halogen atom or alkoxyl group; G₂represents a hydrogen atom, halogen atom, or alkoxyl group which mayhave a substituent; and R₄₃ denotes an alkyl group which may have asubstituent.
 18. The silver halide color photographic material asdescribed in claim 1, further comprising at least one discolorationinhibitor represented by formulas (XVI) and (XVII) ##STR56## wherein R₄₄represents a hydrogen atom, an aliphatic group, an aromatic group, aheterocyclic group, or a substituted silyl group ##STR57## which are thesame or different, each represents aliphatic groups, aromatic groups,aliphatic oxy groups, or aromatic oxy groups; R₄₅, R₄₆, R₄₇, R₄₈, andR₄₉ may be the same or different, each denoting a hydrogen atom, analkyl group, an aryl group, an alkoxyl group, a hydroxyl group, mono- ordialkylamino group, an imino group, and an acylamino group; R₄₄ and R₄₅may combine with each other to form a 5- or 6-membered ring; R₅₀, R₅₁,R₅₂, and R₅₃ may be the same or different, each denoting a hydrogen atomand an alkyl group; X₀ denotes a hydrogen atom, an aliphatic group, anacyl group, an aliphatic or an aromatic sulfonyl group, an aliphatic oran aromatic sulfinyl group, an oxyradical group, or hydroxyl group; andA₀ denotes a group of non-metallic atoms necessary to form a 5-, 6-, or7-membered ring.
 19. The silver halide color photographic material asdescribed in claim 1, further comprising an ultraviolet light absorbentrepresented by formula (XI) ##STR58## wherein R₃₁, R₃₂, R₃₃, R₃₄, andR₃₅, which may be the same or different, each represents a hydrogenatom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenylgroup, aryl group, alkoxyl group, acyloxy group, aryloxy group,alkylthio group, arylthio group, mono- or dialkylamino group, acylaminogroup, or 5- or 6-membered heterocyclic group containing at least oxygenor nitrogen.
 20. The silver halide color photographic material asdescribed in claim 19, comprising 1×10⁻⁴ to 2×10⁻³ mol/m² of saidultraviolet light absorbent.
 21. The silver halide color photographicmaterials as described in claim 18, further comprising at least onecyan, magenta or yellow coupler.
 22. A silver halide color photographicmaterial as described in claim 21, wherein the compound represented byformula (XVI) or (XVII) is used in an amount of 0.5 to 200 wt% based onthe yellow coupler or cyan coupler.
 23. A silver halide colorphotographic material comprising at least one silver halide emulsionlayer having associated therewith at least one compound of the formula:##STR59## wherein R₃ represents a methyl group; R₂₃ and R₂₄ eachrepresents a hydrogen atom or alkyl group, provided that one of R₂₃ andR₂₄ is a hydrogen atom and that both of them are not hydrogen atoms atthe same time.
 24. The silver halide color photographic material asdescribed in claim 23, further comprising at least one cyan, magenta oryellow coupler.
 25. A silver halide color photographic materialcomprising at least one silver halide emulsion layer having associatedtherewith at least one compound represented by formula (X) and at leastone pyrazolone type magenta coupler having at the coupling positionthereof a coupling off group represented by formula (II) ##STR60##wherein R represents an alkyl group or aryl group; and R₂₃ and R₂₄ eachrepresents a hydrogen atom or alkyl group, provided that both of themare not hydrogen atoms or alkyl groups at the same time.